Chapter 1
© 2012 Siva Reddy et al., licensee InTech. This is an open access chapter distributed under the terms of the
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Electronic (Absorption) Spectra of
3d Transition Metal Complexes
S. Lakshmi Reddy, Tamio Endo and G. Siva Reddy
Additional information is available at the end of the chapter
http://dx.doi.org/10.5772/50128
1. Introduction
1.1. Types of spectra
Spectra are broadly classified into two groups (i) emission spectra and (ii) absorption
spectra
i. Emission spectra Emission spectra are of three kinds (a) continuous spectra,(b) band
spectra and (c) line spectra.
Continuous spectra: Solids like iron or carbon emit continuous spectra when they are heated
until they glow. Continuous spectrum is due to the thermal excitation of the molecules of
the substance.
Band spectra: The band spectrum consists of a number of bands of different colours separated
by dark regions. The bands are sharply defined at one edge called the head of the band and
shade off gradually at the other edge. Band spectrum is emitted by substances in the
molecular state when the thermal excitement of the substance is not quite sufficient to break
the molecules into continuous atoms.
Line spectra: A line spectrum consists of bright lines in different regions of the visible
spectrum against a dark background. All the lines do not have the same intensity. The
number of lines, their nature and arrangement depends on the nature of the substance
excited. Line spectra are emitted by vapours of elements. No two elements do ever produce
similar line spectra.
ii. Absorption spectra: When a substance is placed between a light source and a
spectrometer, the substance absorbs certain part of the spectrum. This spectrum is
called the absorption spectrum of the substance.
Advanced Aspects of Spectroscopy
4
Electronic absorption spectrum is of two types. d-d spectrum and charge transfer spectrum.
d-d spectrum deals with the electronic transitions within the d-orbitals. In the charge –
transfer spectrum, electronic transitions occur from metal to ligand or vice-versa.
2. Electronic spectra of transitions metal complexes
Electronic absorption spectroscopy requires consideration of the following principles:
a. Franck-Condon Principle: Electronic transitions occur in a very short time (about 10
-15
sec.) and hence the atoms in a molecule do not have time to change position appreciably
during electronic transition .So the molecule will find itself with the same molecular
configuration and hence the vibrational kinetic energy in the exited state remains the
same as it had in the ground state at the moment of absorption.
b. Electronic transitions between vibrational states: Frequently, transitions occur from the
ground vibrational level of the ground electronic state to many different vibrational levels
of particular excited electronic states. Such transitions may give rise to vibrational fine
structure in the main peak of the electronic transition. Since all the molecules are present
in the ground vibrational level, nearly all transitions that give rise to a peak in the
absorption spectrum will arise from the ground electronic state. If the different excited
vibrational levels are represented as υ
1, υ2, etc., and the ground state as υ0, the fine structure
in the main peak of the spectrum is assigned to υ
0
υ0 , υ0
υ1, υ0
υ2 etc., vibrational
states. The υ
0
υ0 transition is the lowest energy (longest wave length) transition.
c. Symmetry requirement: This requirement is to be satisfied for the transitions discussed
above.
Electronic transitions occur between split ‘d’ levels of the central atom giving rise to so
called d-d or ligand field spectra. The spectral region where these occur spans the near
infrared, visible and U.V. region.
-1
Ultraviolet UV Visible Vis Near infrared NIR
50,000 - 26300 26300 -12800 12800 -5000 cm
200 - 380 380 -780 780 - 2000 nm
3. Russel-Saunders or L-S coupling scheme
An orbiting electronic charge produces magnetic field perpendicular to the plane of the
orbit. Hence the orbital angular momentum and spin angular momentum have
corresponding magnetic vectors. As a result, both of these momenta couple magnetically to
give rise to total orbital angular momentum. There are two schemes of coupling: Russel-
Saunders or L-S coupling and j-j coupling.
a. The individual spin angular momenta of the electrons, s
i, each of which has a value of ±
½, combine to give a resultant spin angular momentum (individual spin angular
momentum is represented by a lower case symbol whereas the total resultant value is
given by a upper case symbol).
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
5
i
s=S
Two spins of each ± ½ could give a resultant value of S =1 or S= 0; similarly a resultant of
three electrons is 1 ½ or ½ .The resultant is expressed in units of h/2 π . The spin multiplicity
is given by (2S+1). Hence, If n is the number of unpaired electrons, spin multiplicity is given
by n + 1.
b. The individual orbital angular momenta of electrons, l
i, each of which may be 0, 1 ,2, 3 ,
4 ….. in units of h/2π for s, p, d, f, g,..orbitals respectively, combine to give a
resultant orbital angular momentum, L in units of h/2π . li = L
The resultant L may be once again 0, 1, 2, 3, 4…. which are referred to as S, P, D, F G,
respectively in units of h/2π.The orbital multiplicity is given by (2L+1).
0 1 2 3 4 5
S P D F G H
c. Now the resultant S and L couple to give a total angular momentum, J. Hence, it is not
surprising that J is also quantized in units of h/2π.The possible values of J quantum
number are given as
J = L + S , L + S - 1 , L + S - 2 , L + S - 3 , ….. L - S ,
The symbol | | indicates that the absolute value (L – S) is employed, i.e., no regard is paid to
± sign. Thus for L = 2 and S = 1, the possible J states are 3, 2 and 1 in units of h/2π.
The individual spin angular momentum, s
i and the individual orbital angular momentum, li,
couple to give
total individual angular momentum, ji. This scheme of coupling is known as
spin-orbit coupling or j -j coupling.
4. Term symbols
4.1. Spectroscopic terms for free ion ground states
The rules governing the term symbol for the ground state according to L-S coupling scheme
are given below:
a. The spin multiplicity is maximized i.e., the electrons occupy degenerate orbitals so as to
retain parallel spins as long as possible (Hund’s rule).
b. The orbital angular momentum is also maximized i.e., the orbitals are filled with
highest positive m values first.
c. If the sub-shell is less than half-filled, J = L– S and if the sub-shell is more than half –
filled, J = L +S.
The term symbol is given by
2S+1
LJ. The left-hand superscript of the term is the spin
multiplicity, given by 2S+1 and the right- hand subscript is given by J. It should be noted
that S is used to represent two things- (a) total spin angular momentum and (b) and total
angular momentum when L = 0. The above rules are illustrated with examples.
Advanced Aspects of Spectroscopy
6
For d
4
configuration:
Hence, L = 3 -1 = 2 i.e., D; S = 2; 2S+1 = 5; and J = L- S = 0; Term symbol =
5
D0
For d
9
configuration:
Hence, L = +2+1+0-1 = 2 i.e., D ; S = 1 /2 ; 2S+1 = 2 ; and J = L+ S = 3/2 ; Term symbol =
2
D5/2
Spin multiplicity indicates the number of orientations in the external field. If the spin
multiplicity is three, there will be three orientations in the magnetic field.- parallel,
perpendicular and opposed. There are similar orientations in the angular momentum in an
external field.
The spectroscopic term symbols for d
n
configurations are given in the Table-1. The terms are
read as follows: The left-hand superscript of the term symbol is read as singlet, doublet,
triplet, quartet, quintet, sextet, septet, octet, etc., for spin multiplicity values of 1, 2, 3, 4, 5, 6,
7, 8, etc., respectively.
1
S0 (singlet S nought);
2
S1/2 (doublet S one–half);
3
P2 (triplet P two );
5
I8
(quintet I eight). It is seen from the Table-1 that d
n
and d
10-n
have same term symbols, if we
ignore J values. Here n stands for the number of electrons in d
n
configuration.
d
n
Term d
n
Term
d
0
d
1
d
2
d
4
d
5
1
S0
2
D3/2
3
F2
5
D0
6
S5/2
d
10
d
9
d
8
d
6
1
S0
2
D5/2
3
F4
5
D4
Table 1. Term symbols
It is also found that empty sub -shell configurations such as p
0
, d
0
, f
0
, etc., and full filled sub-
shell configurations such as p
6
, d
10
, f
14
, etc., have always the term symbol
1
S0 since the
resultant spin and angular momenta are equal to zero. All the inert gases have term symbols
for their ground state
1
S0 .Similarly all alkali metals reduce to one electron problems since
closed shell core contributes nothing to L , S and J; their ground state term symbol is given
by
2
S1/2. Hence d electrons are only of importance in deciding term symbols of transition
metals.
5. Total degeneracy
We have seen that the degeneracy with regard to spin is its multiplicity which is given by
(2S+1). The total spin multiplicity is denoted by M
s running from S to -S. Similarly orbital
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
7
degeneracy, ML, is given by (2L+1) running from L to -L. For example, L= 2 for D state and
so the orbital degeneracy is (2x2+1) =5 fold. Similarly, for F state, the orbital degeneracy is
seven fold. Since there are (2L+1) values of M
L, and (2S+1) values of Ms in each term, the total
degeneracy of the term is given by: 2(L+1)(2S+1).
Each value of M
L occurs (2S+1) times and each value of Ms occurs (2L+1) times in the term.
For
3
F state, the total degeneracy is 3x7 =21 fold and for the terms
3
P,
1
G,
1
D,
1
S, the total
degeneracy is 9,9,5,1 fold respectively. Each fold of degeneracy represents one microstate.
6. Number of microstates
The electrons may be filled in orbitals by different arrangements since the orbitals have
different m
l values and electrons may also occupy singly or get paired. Each different type
of electronic arrangement gives rise to a microstate. Thus each electronic configuration will
have a fixed number of microstates. The numbers of microstates for p
2
configuration are
given in Table-2 (for both excited and ground states).
ml
-1
0
+1
mL +1 0 -1 +1 0 -1 +1 0 -1 +1 +1 -1 +2 0
Table 2. Number of microstates for p
2
configuration
Each vertical column is one micro state. Thus for p
2
configuration, there are 15 microstates.
In the above diagram, the arrangement of singlet states of paired configurations given in A
(see below) is not different from that given in B and hence only one arrangement for each ml
value.
The number of microstates possible for any electronic configuration may be calculated from
the formula,
Number of microstates = n! / r! (n - r)!
Where n is the twice the number of orbitals, r is the number of electrons and ! is the factorial.
For p
2
configuration, n= 3x2 =6; r = 2; n – r = 4
6! = 6 x 5 x 4 x 3 x 2 x 1 = 720; 2! = 2 x 1 =2; 4! = 4 x 3 x 2 x 1 = 24
Substituting in the formula, the number of microstates is 15.
Advanced Aspects of Spectroscopy
8
Similarly for a d
2
configuration, the number of microstates is given by 10! / 2! (10 – 2)!

10987654321
45
2187654321


Thus a d
2
configuration will have 45 microstates. Microstates of different d
n
configuration
are given in Table-3.
d
n
configuration
d
1
,d
9
d
2
,d
8
d
3
,d
7
d
4
,d
6
d
5
d
10
No.of microstates 10 45 120 210 252 1
Table 3. Microstates of different d
n
configuration
7. Multiple term symbols of excited states
The terms arising from d
n
configuration for 3d metal ions are given Table-4.
Configuration Ion Term symbol
d
1
d
9
d
2
d
8
d
3
d
7
d
4
d
6
d
5
d
10
Ti
3+
,V
4+
Cu
2+
Ti
2+
,V
3+
,Cr
4+
Ni
2+
Cr
3+
,V
2+
,Mn
4+
Ni
3+
,Co
2+
Cr
2+
,Mn
3+
Fe
2+
,Co
3+
Mn
2+
, Fe
3+
Zn
2+
2
D
3
F,
3
P,
1
G,
1
D,
1
S
4
F,
4
P,
2
( H, G, F, D, D, P)
5
D ,
3
( H, G, F, F, , D, P, P ),
1
(I, ,G, G, F, D, D, S,S)
6
S,
4
(G, F, D, P),
2
(I, H, G, G, F, F),
2
(D, D, D, P, S)
6
S
Table 4. Terms arising from d
n
configuration for 3d ions (n=1 to10)
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
9
8. Selection rules
8.1. La Porte selection rule
This rule says that transitions between the orbitals of the same sub shell are forbidden. In
other words, the for total orbital angular momentum is Δ L = ± 1. This is La Porte allowed
transitions. Thus transition such as
1
S
1
P and
2
D
2
P are allowed but transition such as
3
D
3
S is forbidden since Δ L = -2 .That is, transition should involve a change of one unit of
angular momentum. Hence transitions from gerade to ungerade (g to u) or vice versa are
allowed, i.e., u
g or g
u but not u
u or g
g. In the case of p sub shell, both ground
and excited states are odd and in the case of d sub shell both ground and excited states are
even. As a rule transition should be from even to odd or vice versa.
The same rule is also stated in the form of a statement instead of an equation:
Electronic transitions within the same p or d sub-shell are forbidden, if the molecule has centre of
symmetry.
8.2. Spin selection rule
The selection Rule for Spin Angular Momentum is
Δ S = 0
Thus transitions such as
2
S
2
P and
3
D
3
P are allowed, but transition such as
1
S
3
P is
forbidden. The same rule is also stated in the form of a statement,
Electronic Transitions between the different states of spin multiplicity are forbidden.
The selection Rule for total angular momentum, J, is
Δ J = 0 or ± 1
The transitions such as
2
P1/2
2
D3/2 and
2
P3/2
2
D3/2 are allowed, but transition such as
2
P1/2
2
D5/2 is forbidden since Δ J= 2.
There is no selection rule governing the change in the value of n, the principal quantum
number. Thus in hydrogen, transitions such as 1s
2p, 1s
3p, 1s
4p are allowed.
Usually, electronic absorption is indicated by reverse arrow,
, and emission is indicated by
the forward arrow,
, though this rule is not strictly obeyed.
8.3. Mechanism of breakdown of selection rules
8.3.1. Spin-orbit coupling
For electronic transition to take place, Δ S = 0 and Δ L= ± 1 in the absence of spin-orbit coupling.
However, spin and orbital motions are coupled. Even, if they are coupled very weakly, a little of
each spin state mixes with the other in the ground and excited states by an amount dependent
Advanced Aspects of Spectroscopy
10
upon the energy difference in the orbital states and magnitude of spin –orbit coupling constant.
Therefore electronic transitions occur between different states of spin multiplicity and also
between states in which Δ L is not equal to
± 1. For example, if the ground state were 99%
singlet and 1% triplet (due to spin– orbit coupling) and the excited state were 1% singlet and 99
% triplet, then the intensity would derive from the triplet –triplet and singlet-singlet
interactions. Spin-orbit coupling provides small energy differences between degenerate state.
This coupling is of two types. The single electron spin orbit coupling parameter ζ, gives the
strength of the interaction between the spin and orbital angular momenta of a single
electron for a particular configuration. The other parameter, λ, is the property of the term.
For high spin complexes,
2S

Here positive sign holds for shells less than half field and negative sign holds for more than
half filled shells. S is the same as the one given for the free ion. The λ values in crystals are
close to their free ion values. Λ decreases in crystal with decreasing Racah parameters B and
C. For high spin d
5
configuration, there is no spin orbit coupling because
6
S state is
unaffected by the ligand fields. The λ and ζ values for 3d series are given in Table-5.
Ion Ti(II) V(II) Cr(II) Mn(II) Fe(II) Co(II) Ni(II)
Ξ (cm
-1
) 121 167 230 347 410 533 649
λ(cm
-1
) 60 56 57 0 -102 -177 -325
Table 5. λ and ζ values for 3d series
8.3.2. La Porte selection rule
Physically 3d (even) and 4p (odd) wave functions may be mixed, if centre of inversion (i) is
removed. There are two processes by which i is removed.
a. The central metal ion is placed in a distorted field (tetrahedral field, Tetragonal
distortions, etc.,) The most important case of distorted or asymmetric field is the case of
a tetrahedral complex. Tetrahedron has no inversion centre and so d-p mixing takes
place. So electronic transitions in tetrahedral complexes are much more intense, often
by a factor 100, than in a analogous octahedral complexes. Trans isomer of [Co(en)2Cl2]
+
in aqueous solution is three to four times less intense than the
cis isomer because the
former is centro-symmetric. Other types of distortion include Jahn –Teller distortions.
b. Odd vibrations of the surrounding ligands create the distorted field for a time that is long
enough compared to the time necessary for the electronic transition to occur (Franck
Condon Principle).Certain vibrations will remove the centre of symmetry. Mathematically
this implies coupling of vibrational and electronic wave functions. Breaking down of La
Porte rule by vibrionic coupling has been termed as “Intensity Stealing”. If the forbidden
excited term lies energetically nearby a fully allowed transition, it would produce a very
intense band. Intensity Stealing by this mechanism decreases in magnitude with
increasing energy separation between the excited term and the allowed level.
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
11
9. Splitting of energy states
The symbols A(or a) and B (or b) with any suffixes indicate wave functions which are singly
degenerate. Similarly
E (or e) indicates double degeneracy and T (or t) indicates triple
degeneracy. Lower case symbols,
a1g, a2g, eg, etc., are used to indicate electron wave
functions(orbitals) and upper case symbols are used to describe electronic energy levels.
Thus
2
T2g means an energy level which is triply degenerate with respect to orbital state and
also doubly degenerate with respect to its spin state. Upper case symbols are also used
without any spin multiplicity term and they then refer to symmetry (ex.,
A1g symmetry). The
subscripts
g and u indicate gerade (even) and ungerade (odd).
d orbitals split into two sets - t2g orbitals and eg orbitals under the influence crystal field.
These have
T2g and Eg symmetry respectively. Similarly f orbitals split into three sets - a2u
(
fxyz) , t2u (fx (y
2
- z
2
) , fy (z
2
-x
2
), fz (x
2
-y
2
) and t1u ( fx
3
, fy
3
, fz
3
). These have symmetries A2u, T2u and T1u
respectively.
Splitting of
D state parallels the splitting of d orbitals and splitting of F state splits
parallels splitting of
f orbitals. For example, F state splits into either T1u, T2u and A2u or
T1g, T2g and A2g sub-sets. Which of these is correct is determined by g or u nature of the
configuration from which
F state is derived. Since f orbitals are u in character
2
F state
corresponding to
f
1
configuration splits into
2
T1u,
2
T2u, and
2
A2u components; similarly
3
F
state derived from
d
2
configuration splits into
3
T2g,
3
T1g and
3
A2g components because d
orbitals are
g in character.
9.1. Splitting of energy states corresponding to d
n
terms
These are given in Table-6.
Energy Sub- states
S
A1
P
T1
D E + T2
F
A2+ T1+ T2
G A1 + E + T1 + T2
H E + T1 + T1 + T2
I A1 + A2 + E + T1 + T2 + T2
Table 6. Splitting of energy states corresponding to d
n
terms
The d-d spectra is concerned with d
n
configuration and hence the crystal field sub-states are
given for all the d
n
configuration in Table -7.
Advanced Aspects of Spectroscopy
12
Configuration
Free ion
ground state
Crystal field
substates
Important
excited
states
Crystal field
state
d
1
, d
9
d
2
, d
8
d
3
, d
7
d
4
, d
6
d
5
2
D
3
F
4
F
5
D
6
S
2
T2g,
2
Eg
3
T1g,
3
T2g,
3
A2g
4
T1g,
4
T2g,
4
A2g
5
T2g,
5
Eg
6
A1g
3
P
4
p
3
T1g
4
T1g
Table 7. Crystal field components of the ground and some excited states of d
n
(n=1 to 9) configuration
10. Energy level diagram
Energy Level Diagrams are described by two independent schemes - Orgel Diagrams which
are applicable to weak field complexes and Tanabe –Sugano (or simply T-S) Diagrams
which are applicable to both weak field and strong field complexes.
11. Inter-electronic repulsion parameters
The inter-electronic repulsions within a configuration are linear combinations of Coulombic
and exchange integrals above the ground term. They are expressed by either of the two
ways: Condon - Shortley parameters, F
0, F2 and F4 and Racah parameters, A, B and C. The
magnitude of these parameters varies with the nature of metal ion.
11.1. Racah parameters
The Racah parameters are A, B and C. The Racah parameter A corresponds to the partial
shift of all terms of a given electronic configuration. Hence in the optical transition
considerations, it is not taken into account. The parameter, B measures the inter electronic
repulsion among the electrons in the d-orbitals. The decrease in the value of the
interelectronic repulsion parameter, B leads to formation of partially covalent bonding.
The ratio between the crystal B
1
parameter and the free ion B parameter is known as
nephelauxetic rato and it is denoted by β. The value of β is a measure of covalency. The
smaller the value, the greater is the covalency between the metal ion and the ligands. The
B and C values are a measure of spatial arrangement of the orbitals of the ligand and the
metal ion.
Racah redefined the empirical Condon –Shortley parameters so that the separation between
states having the maximum multiplicity (for example, difference between is a function of
3
F
and
3
P or
4
F and
4
P is a function of a single parameter, B. However, separations between
terms of different multiplicity involve both B and C
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
13
12. Tanabe –Sugano diagrams
Exact solutions for the excited sate energy levels in terms of Dq, B and C are obtained from
Tanabe-Sugano matrices. However, these are very large (10 x 10) matrices and hand
calculations are not feasible. For this reason Tanabe-Sugano have drawn energy level
diagrams known as T-S diagrams or energy level diagrams. The T-S diagrams are valid only
if the value of B, C and Dq ae lower for a complex than for the free ion value.
Quantitative interpretation of electronic absorption spectra is possible by using Tanabe –
Sugano diagrams or simply T-S diagrams. These diagrams are widely employed to correlate
and interpret spectra for ions of all types, from d
2
to d
8
. Orgel diagrams are useful only
qualitatively for high spin complexes whereas T-S diagrams are useful both for high spin
and low spin complexes. The x-axis in T-S diagrams represent the ground state term.
Further, in T-S diagrams, the axes are divided by B, the interelectronic repulsion parameter
or Racah Parameter. The x-axis represents the crystal field strength in terms of Dq/ B or Δ / B
and the Y-axis represents the energy in terms of E/B.
The energies of the various electronic states are given in the T-S diagrams on the vertical
axis and the ligand field strength increases from left to right on the horizontal axis. The
symbols in the diagram omit the subscript, g, with the understanding that all states are
gerade states. Also, in T.S. diagrams, the zero of energy for any particular d
n
ion is taken to
be the energy of the ground state. Regardless of the ligand field strength, then, the
horizontal axis represents the energy of the ground state because the vertical axis is in units
of E/B and x-axis is also in units of Δ /B. Thus, the unit of energy in T-S diagram is B, Racah
Parameter.
The values of B are different for different ions of the same d
n
(or different d
n
configuration)
which is shown on the top of each diagram. One T-S diagram is used for all members of an
isoelectronic group. Also some assumption is made about the relative value of C/B.
13. Electron spin resonance
Electron Spin Resonance (ESR) is a branch of spectroscopy in which radiation of
microwave frequency is absorbed by molecules possessing electrons with unpaired spins.
It is known by different names such as Electron Paramagnetic Resonance (EPR), Electron
Spin Resonance (ESR) and Electron Magnetic Resonance (EMR). This method is an
essential tool for the analysis of the structure of molecular systems or ions containing
unpaired electrons, which have spin-degenerate ground states in the absence of magnetic
field. In the study of solid state materials, EPR method is employed to understand the
symmetry of surroundings of the paramagnetic ion and the nature of its bonding to the
nearest neighbouring ligands.
When a paramagnetic substance is placed in a steady magnetic field (H), the unpaired
electron in the outer shell tends to align with the field. So the two fold spin degeneracy is
Advanced Aspects of Spectroscopy
14
removed. Thus the two energy levels, E1/2 and E-1/2 are separated by gH, where g is
spectroscopic splitting factor and is called gyro magnetic ratio and
is the Bohr magneton.
Since there is a finite probability for a transition between these two energy levels, a change
in the energy state can be stimulated by an external radio frequency. When microwave
frequency (
) is applied perpendicular to the direction of the field, resonance absorption will
occur between the two split spin levels. The resonance condition is given by, h
= gH,
where h is Planck’s constant.
The resonance condition can be satisfied by varying
or H. However, EPR studies are
carried out at a constant frequency (
), by varying magnetic field (H). For a free electron, the
g value is 2.0023. Since h and
are constants, one can calculate the g factor. This factor
determines the divergence of the Zeeman levels of the unpaired electron in a magnetic field
and is characteristic of the spin system.
In the crystal systems, the electron spins couple with the orbital motions and the g value is a
measure of the spin and orbital contributions to the total magnetic moment of the unpaired
electron and any deviation of magnetic moment from the free spin value is due to the spin-
orbit interaction. It is known that the crystal field removes only the orbital degeneracy of the
ground terms of the central metal ion either partially or completely. The strong electrical
fields of the surrounding ligands results in “Stark Splitting” of the energy levels of the
paramagnetic ion. The nature and amount of splitting strongly depends on the symmetry of
the crystalline electric field. The Stark splitting of the free ion levels in the crystal field
determines the magnetic behaviour of the paramagnetic ion in a crystal. Whenever there is a
contribution from the unquenched orbital angular momentum, the measured g values are
isotropic as a result of the asymmetric crystal field since the contribution from the orbital
motion is anisotropic. To decide the ultimate ground state of a paramagnetic ion in the
crystal, the two important theorems, Kramers and Jahn-Teller, are useful. Using group
theory, one can know the nature of the splitting of the free ion levels in the crystal fields of
various symmetries.
Jahn-Teller theorem states that any nonlinear molecule in an electronically degenerate
ground state is unstable and tends to distort in order to remove this degeneracy. The
direction of distortion which results in greatest stabilization can often be deduced from EPR
and other spectroscopic data.
Kramers’ theorem deals with restrictions to the amount of spin degeneracy which can be
removed by a purely electrostatic field. If the system contains an odd number of electrons,
such an electrostatic field cannot reduce the degeneracy of any level below two. Each pair
forms what is known as a Kramers’ doublet, which can be separated only by a magnetic
field. For example, Fe(III) and Mn(II) belonging to d
5
configuration, exhibit three Kramers’
doublets labeled as
5/2, 3/2 and 1/2.
If the central metal ion also possesses a non-zero nuclear spin, I, then hyperfine splitting
occurs as a result of the interaction between the nuclear magnetic moment and the electronic
magnetic moment. The measurement of g value and hyperfine splitting factor provides
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
15
information about the electronic states of the unpaired electrons and also about the nature of
the bonding between the paramagnetic ion and its surrounded ligands. If the ligands also
contain non-zero nuclear spin, then the electron spin interacts with the magnetic moment of
the ligands. Then one could expect super hyperfine EPR spectrum.
The g value also depends on the orientation of the molecules having the unpaired electron
with respect to the applied magnetic field. In the case of perfect cubic symmetry, the g
value does not depend on the orientation of the crystal. But in the case of low symmetry
crystal fields, g varies with orientation. Therefore we get three values g
xx, gyy, and gzz
corresponding to a, b and c directions of the crystal. In the case of tetragonal site gxx = gyy
which is referred to as g
and corresponds to the external magnetic field perpendicular to
the Z-axis. When it is parallel, the value is denoted as g

. Hence one can deduce the
symmetry of a complex by EPR spectrum i.e., cubic, tetragonal, trigonal or orthorhombic.
Anyhow, it is not possible to distinguish between orthorhombic and other lower
symmetries by EPR.
13.1. EPR signals of first group transition metal ions
Transition metal ions of 3d group exhibit different patterns of EPR signals depending on
their electron spin and the crystalline environment. For example, 3d
1
ions, VO
2+
and Ti
3+
have s = 1/2 and hence are expected to exhibit a single line whose g value is slightly below
2.0. In the case of most abundant
51
V, s = 1/2 and I = 7/2, an eight line pattern with hyperfine
structure of almost equal intensity can be expected as shown in Fig-1. In the case of most
abundant Ti, (s = 1/2 and I = 0), no hyperfine structure exists. However, the presence of less
abundant isotopes (
47
Ti with I = 5/2 and
49
Ti with I = 7/2) give rise to weak hyperfine
structure with six and eight components respectively. This weak structure is also shown in
Fig-1.
Cr(III), a d
3
ion, with s = 3/2 exhibits three fine line structure. The most abundant
52
Cr has
I = 0 and does not exhibit hyperfine structure. However,
53
Cr with I = 3/2 gives rise to
hyperfine structure with four components. This structure will be weak because of the low
abundance of
53
Cr. Thus each one of the three fine structure lines of
53
Cr is split into four
weak hyperfine lines. Of these, two are overlapped by the intense central line due to the
most abundant
52
Cr and the other two lines are seen in the form of weak satellites.
Mn(II) and Fe(III) with d
5
configuration have s = 5/2 and exhibit five lines which correspond
to a
5/2 3/2, 3/2 1/2 and +1/2 -1/2 transitions. In the case of
55
Mn,
which has I = 5/2, each of the five transitions will give rise to a six line hyperfine structure.
But in powders, usually one observes the six-hyperfine lines corresponding to
+1/2 -
1/2
transition only. The remaining four transition sets will be broadened due to the high
anisotropy. Fe
3+
yields no hyperfine structure as seen in Fig -1.
Co
2+
, a d
7
configuration, with s value of 3/2 exhibits three fine structure lines. In the case of
59
Co (I = 7/2), eight line hyperfine pattern can be observed as shown in the Fig-1.
Advanced Aspects of Spectroscopy
16
Figure 1. EPR signal of 3d ions
14. Survey of experimental results
14.1. Titanium
Titanium is the ninth most abundant element in the Earth's crust (0.6%). There are 13 known
isotopes of titanium. Among them five are natural isotopes with atomic masses 46 to 50 and
the others are artificial isotopes. The synthetic isotopes are all radioactive. Titanium alloys are
used in spacecraft, jewelry, clocks, armored vehicles, and in the construction of buildings. The
compounds of titanium are used in the preparation of paints, rubber, plastics, paper, smoke
screens (TiCl
4 is used), sunscreens. The main sources of Ti are ilmenite and rutile.
Titanium exhibits +1 to +4 ionic states. Among them Ti
4+
has d
0
configuration and hence has
no unpaired electron in its outermost orbit. Thus Ti
4+
exhibits diamagnetism. Hence no d-d
transitions are possible. The ionic radius of Ti
3+
is the same as that of Fe(II) (0.76 A.U). Ti(I)
and Ti(III) have unpaired electrons in their outermost orbits and exhibit para magnetism
14.2. Electronic spectra of titanium compounds
The electronic configuration of Ti
3
is [Ar] 3d
1
4s
2
. It has five fold degeneracy and its ground
state term symbol is
2
D. In an octahedral crystal field, the five fold degeneracy is split into
2
T2g
and
2
Eg states. Thus only one single electron transition,
2
T2g
2
Eg, is expected in an
octahedral crystal field. The separation between these energies is 10Dq, which is crystal field
energy.
Normally, the ground
2
T2g
state is split due to Jahn-Teller effect and hence lowering
of symmetry is expected for Ti(III) ion. This state splits into
2
B2g and
2
Eg states in tetragonal
symmetry and the excited term
2
Eg also splits into
2
B1g and
2
A1g levels. Thus, three bands are
expected for
tetragonal (C4v) symmetry. Energy level diagram in tetragonal environment is
shown in Fig -2.
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
17
Figure 2. Energy level diagram of Ti
3+
in octahedral and tetragonal fields
The transitions in the tetragonal field are described by the following equations.
22
2
:4 4 4 2 3 5
gg
B E Dq Ds Dt Dq Ds Dt Ds Dt



(1)
2
21
:6 2 4 2 10
gg
B B Dq Ds Dt Dq Ds Dt Dq



(2)
22
21
:6 2 6 4 2 10 4 5
gg
B A Dq Ds Dt Dq Ds Dt Dq Ds Dt



(3)
In the above formulae, Dq is octahedral crystal field and Ds and Dt are tetragonal field
parameters. The same sign of Dq and Dt indicates an axial elongation and opposite sign
indicates an axial compression
14.2.1. EPR spectra of titanium compounds
When any Ti(III) compound in the form of powder is placed in a magnetic field, it gives a
resonance signal. The single d-electron of Ti
3+
has spin, s = 1/2. The abundance of isotopes is
reported as
46
Ti 87%,
48
Ti 7.7% and
50
Ti 5.5% and have nuclear spin I = 0, 5/2 and 7/2
respectively. Electron spin and nuclear spin interactions give rise to (2I+1) hyperfine lines
(0,6 and 8) and appear as satellite. Since
46
Ti abundance is more, the EPR signal contains
only one resonance line which is similar to the one shown in Fig-3. The g value for this
resonance is slightly less than 2.0.
Figure 3. RT powered EPR spectrum of Ti(III).
14.2.2. Relation between EPR and optical absorption spectra
EPR studies for Ti
3+
can be correlated with optical data to obtain the orbital reduction
parameter.
Advanced Aspects of Spectroscopy
18



11
Covalency
e
Ionic ionic
g
gE
K
n


(4)
where n is 8 for C
4V ,
E
is the energy of appropriate transition, λ is the spin-orbit coupling
constant for Ti
3+
, i.e., 154 cm
-1
and k is the orbital reduction parameter.
14.2.3. Typical examples
EPR and optical absorption spectral data of selected samples are discussed as examples. The
data chosen from the literature are typical for each sample and hence should be considered
as representative only. For more complete information on specific example, the original
references are to be consulted. X-band spectra and optical absorption spectra of the
powdered samples are recorded at room temperature (RT).
14.2.4. Optical absorption studies
Ti(III) ion in solids is characterized by three broad bands around 7000, 12000 and 18000 cm
-1
.
These are due to the transitions from
2
B2g
2
Eg,
2
B2g
2
B1g, and
2
B2g
2
A1g respectively. Three
bands of titanite at 7140, 13700 and 16130 cm
-1
and of anatase at 6945, 12050 and 18180 cm
-1
are
attributed to the above transitions. The optical absorption spectrum of lamprophyllite is also
similar. The optical absorption spectrum of benitoite sample displays three bands at 8260,
10525 and 15880 cm
-1
. From the observed band positions, the crystal field parameter in
octahedral field, Dq and tetragonal field parameters, Ds and Dt, are given in Table-8.
Sample Dq cm
-1
Ds cm
-1
Dt cm
-1
Titanite 1370 -1367 608
Anatase 1205 -1867 268
Lamprophyllite 877 -1426 1525
Benitoite 1050 -1945 485
Table 8. Crystal field parameters of Ti(III)
The magnitude of Dt indicates the strength of the tetragonal distortion. This is more in
lamprophyllite when compared to the other samples.
i.
X-band EPR spectra of the powdered sample of titanite shows a broad resonance line in
the centre (335.9 mT). The measured g value is 1.957. Another resonance line is noticed
at 341.4 mT with g =1.926. The central eight line transition is superimposed on the
spectrum and the components are attributed to VO(II) impurity. The g value of Ti
3+
is
1.957 and other g value is due to VO(II). The g value of 1.95 indicates that Ti
3+
is in
tetragonally distorted octahedral site.
ii.
The EPR spectrum of anatase shows a large number of resonances centered around g
value of 2 which is attributed to Ti
3+
. The additional structures between g values of 2
and 4 are attributed to Fe(III) impurity in the compound. Both the ions are in
tetragonally distorted environment.
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
19
iii. X band EPR of polycrystalline lamprophyllite sample indicates a broad resonance line
with line width 56.6 mT and a g value of 2.0. This is due to the presence of Ti(III) in the
compound. The broad line is due to the dipolar-dipolar interaction of Ti(III) ions. Even
at liquid nitrogen temperature, only the line intensity increases indicating that Curie
law is obeyed.
Using EPR and optical absorption spectral results of titanite, the covalency parameter is
calculated using equation (4),

11e
ionic
g
gE
n
. The α value obtained is 0.51, which indicates
higher covalent character between ligand and metal ion.
15. Vanadium
Vanadium abundance in earth's crust is 120 parts per million by weight. Vanadium's ground
state electron configuration is [Ar] 3d
3
4s
2
. Vanadium exhibits four common oxidation states
+5, +4, +3, and +2 each of which can be distinguished by its color. Vanadium(V) compounds
are yellow in color whereas +4 compounds are blue, +3 compounds are green and +2
compounds are violet in colour. Vanadium is used in making specialty steels like rust
resistant and high speed tools. The element occurs naturally in about 65 different minerals
and in fossil fuel deposits. Vanadium is used by some life forms as an active center of
enzymes. Vanadium oxides exhibit intriguing electrochemical, photochemical, catalytical,
spectroscopic and optical properties. Vanadium has 18 isotopes with mass numbers varying
from 43 to 60. Of these,
51
V, natural isotope is stable:
15.1. Electronic spectra of vanadium compounds
Vanadium in its tetravalent state invariably exists as oxo-cation, VO
2+
(vanadyl). The VO
2+
ion
has a single d electron which gives rise to the free ion term
2
D. In a crystal field of octahedral
symmetry, this electron occupies the t
2g orbital and gives rise to ground state term
2
T2g. When
the electron absorbs energy, it is excited to the e
g orbital and accordingly in octahedral
geometry only one band corresponding to the transition,
2
T2g
2
Eg, is expected. Because of the
non-symmetrical alignment of the V=O bond along the axis, the site symmetry, in general, is
lowered to tetragonal (C
4V) or rhombic (C2V) symmetry. In C4V site symmetry,
2
T2g splits into
2
B2g and
2
Eg, whereas
2
Eg
splits into
2
B1g,
2
A1g.
Hence three bands are expected in C4V symmetry
in the range of 11000 –14000, 14500 – 19000 and 20000 – 31250 cm
-1
. The degeneracy of
2
Eg is
also removed in C
2V symmetry resulting four bands. Energy level diagram of VO
2+
in
octahedral C
4V
and
C2V symmetries are shown in Fig- 4. In the tetragonal C4V symmetry
transitions are described by the following equations.
22
2
:4 4 4 2 3 5
gg
B E Dq Ds Dt Dq Ds Dt Ds Dt



(5)
2
21
:6 2 4 2 10
gg
B B Dq Ds Dt Dq Ds Dt Dq



(6)
Advanced Aspects of Spectroscopy
20
22
21
:6 2 6 4 2 10 4 5
gg
B A Dq Ds Dt Dq Ds Dt Dq Ds Dt



(7)
In the above formulae, Dq is octahedral crystal field parameter and Ds, Dt are tetragonal
field parameters. The same sign of Dq and Dt indicates an axial elongation and opposite
sign indicates an axial compression.
Figure 4. Energy level diagram indicating the assignment of the transitions in octahedral C4V symmetry.
15.2. EPR spectra of vanadium compounds
The EPR signal is of three types. (i) is due to high concentration of vanadium. If the
vanadium content in the compound is high, it gives a broad resonance line. Therefore the
hyperfine line from
51
V cannot be resolved. The g value for this resonance is less than 2. (ii)
VO
2+
ion has s= ½ and I = 7/2. The EPR spectrum shows hyperfine pattern of eight
equidistant lines. In C
4v symmetry two sets of eight lines are expected (sixteen-line pattern)
whereas in C
2v symmetry three sets of eight lines are expected. Further in tetragonal
distortion,
11
g
<
g
< ge which shows the presence of an unpaired electron in the
xy
d orbital.
This is characteristic feature of a tetragonally compressed complex.
Further lowering of symmetry gives rise to EPR spectrum which is similar to the one shown in
g
yy and gzz respectively. The hyperfine constants are designated as A1, A2 and A3 respectively.
Using the EPR data, the value of dipolar term P and k term are calculated,

11 11
43
77
ee
AP kgg gg

(8)
211
714
e
AP k gg


(9)
 
11 11
an
11
22
33
d
g
gg AAA

(10)
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
21
Using the EPR data, the admixture coefficients are calculated from the following formulae,
22 2
11 1 2 3
23 2
g
CC C (11)
222
12 3 1 2 3
and41g CCC CCC
 (12)


2
11 11 3 1 2 3
15 3
12 1
77
APg k C CCC




(13)
12
11 9
2
14 7
Ap g CCk





(14)
15.3. Relation between EPR and optical absorption spectra
The optical absorption results and EPR results are related as follows. EPR studies can be
correlated with optical data to obtain the orbital coefficients
*2
and
*2
.
*2
11
8
e
xy
gg
E

(15)
*2
1
2
e
xz
gg
E

(16)
Here g
11 and g
are the spectroscopic splitting factors parallel and perpendicular to the
magnetic field direction of g
e (i.e., 2.0023 for a free electron).
E1 is the energy of
2
B2g
2
B1g and
E2 is the energy of
2
B2g
2
Eg.
λ is the spin-orbit coupling constant(160 cm
-1
) for the free vanadium(VO
2+
).
15.4. Typical examples
EPR and optical absorption spectral data of certain selected samples are discussed. The data
chosen from the literature are typical for each sample. The data should be considered as
representative only. For more complete information on specific example, original references
are to be consulted. X-band spectra of the powdered samples and optical absorption spectra
are recorded at room temperature (RT).
X-band EPR spectra of the vanadium(IV) complex with DMF recorded in solutions reveal a
well-resolved axial anisotropy with 16-line hyperfine structure. This is characteristic of an
interaction of vanadium nuclear spin (
51
V, I = 7/2) with S. The observed EPR parameters are
g
11 =1.947, A11 = 161.3 x 10
-4
cm
-1
and g=1.978, A= 49.0 x 10
-4
cm
-1
. EPR parameters of
several samples are available in literature and some of them are given in Table -9.
Advanced Aspects of Spectroscopy
22
Mineral name
11
g
g
11
A
mT
A
mT
Kainite
Apophyllite
Pascoite site I
siteII
CAPH
1.932
1.933
1.933
1.946
1.933
1.983
1.982
1.988
1.976
1.993
17.7
18.02
18.50
20.00
6.9
6.02
7.6
8.2
Table 9. Various EPR parameters of VO(II) in minerals
Using the EPR data, the admixture coefficients are calculated for apophyllite and pascoite
minerals and are given in the Table -10.
Sample C1 C2 C3 K P (x 10
-4
cm
-1
)
Apophyllite 0.7083 0.7124 0.0028 0.86 122.7
Pascoite 0.7010 0.7116 0.0035 0.36 118.4
0.7090 0.7285 0.03174 0.34 143
Table 10. Admixture coefficients of VO
2+
ion
EPR spectrum of polycrystalline sample of wavellite with sixteen line pattern indicates the
presence of VO
2+
ion as an impurity. The EPR parameters calculated are gzz= 1.933 and
g
yy=gxx = 1.970 and the corresponding A values are 19.0 and 6.2 mT.
15.5. Typical examples
a. (i) Divalent vanadium (V
2+
) of d
3
configuration, containing halide and other ions
in aqueous solutions, gives three transitions, i.e.,
4
A2g
4
T2g,
4
A2g
4
T1g(F) and
4
A2g
4
T1g(P) in an octahedral geometry. In

2
2
6
VHO
, the three bands are observed
at 11400, 17100 and 24000 cm
-1
along with some weak shoulders at about 20000 and
22000 cm
-1
. The bands observed at 11400, 17100 and 24000 cm
-1
are assigned to the
transitions
4
A2g
4
T2g,
4
T1g(F) and
4
T1g(P) respectively. 10Dq is 11400 cm
-1
. For divalent
vanadium ion, Racah parameters are B = 860 and C = 4165 cm
-1
. Calculated Racah
parameters are expected to be less than the one in the free ion value. Accordingly, the
weak shoulders observed at 20000 and 22000 cm
-1
are assigned to
4
A2g
2
T2g, and
4
A2g
2
T1g,
2
E transitions.
(ii) The optical absorption spectrum of vanadium carboxylate tetrahydrate sample
displays three bands at 11400, 17360 and 23920 cm
-1
. These are assigned to the
transitions,
4
A2g
4
T2g,
4
T1g(F) and
4
T1g(P) in an octahedral geometry.
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
23
b. Trivalent Vanadium (V
3+
) (d
2
) in aqueous solutions shows two stronger bands at about
15000 and 23000 cm
-1
and some weaker bands at 11500, 18000 cm
-1
. The stronger bands
are assigned to the transitions,
3
T1g(F)
3
T2g(F) and
3
T1g(F)
3
T1g(P) in an octahedral
environment. Since this ion contains two d electrons, it is not so easy to attribute to the
other bands. Therefore T-S diagrams are used to identify the other bands. 10Dq is 16400
cm
-1
and B = 623 (free ion B= 886 cm
-1
and C =765 cm
-1
). Third band could be expected at
32000 cm
-1
due to
3
T1g(F)
2
A1g. This band corresponds to double electron transition
and hence the intensity is expected to be lower than that of the first two bands. The
weaker bands observed at 11500, 18000 cm
-1
are attributed to the spin forbidden
transitions,
3
T1g(F)
1
Eg,
1
T2g
and
1
A1g.
c.
(i) Tetravalent vanadium (V
4+
) (d
1
). The absorption spectrum of tetravalent vanadium
compounds shows three transitions,
2
B2g
2
Eg,
2
B2g
2
B1g and
2
B2g
2
A1g. The
2
B2g
2
Eg
is the most intense and
2
B2g
2
B1g is the weakest. Accordingly, the bands observed in
vanadium doped zinc hydrogen maleate tetrahydrate (ZHMT) at 13982, 16125 and
21047 cm
-1
are assigned to the above three transitions respectively. The octahedral
crystal field parameter, Dq (1613 cm
-1
), and tetragonal field parameters, Ds (-2700 cm
-1
)
and Dt (1178 cm
-1
), are evaluated.
(ii) The electronic absorption spectrum of the VO
2+
in CdSO4.8H2O recorded at room
temperature shows bands at 12800, 13245, 14815, 18345 cm
-1
. These bands are
assigned to
2
B2g
2
Eg,
2
B2g
2
B1g and
2
B2g
2
A1g transitions. The band observed at 12500
cm
-1
is the split component of the band at 13245 cm
-1
. The crystal field octahedral
parameter, Dq (1465 cm
-1
)
and tetragonal field parameters, Ds (-2290 cm
-1
) and Dt
(1126 cm
-1
) are evaluated.
Several examples are found in the literature. Some of them are given in the Table-11.
Sample
Transition from
2
B2
cm
-1
Dq cm
-1
Ds cm
-1
Dt cm
-1
2
E,
2
B1
2
A1
Cadmium
ammonium
phosphate
hexahydradate(C
APH)
12270 16000 26625 1600 -3275 488
Aphophyllite 12500 15335 24385 1538 -2080 653
Pascoite site I
Site II
12255
12255
14450
16000
21415
21415
1445
1600
-2765
-2524
803
937
Table 11.
d. Pentavalent vanadium has no d electron and hence d-d transitions are not possible.
Therefore, the observed bands in electronic absorption spectrum are ascribed to charge
transfer bands. These appear around 37000, 45000 cm
-1
. These are assigned to transitions
from ligand orbitals to metal d-orbitals: A
1
T2 (t1
2e) and A1
T2 (3t2
2e) in
tetrahedral configuration for the ion
3
4
VO
.
Advanced Aspects of Spectroscopy
24
Vanadium doped silica gel also shows sharp band at 41520 cm
-1
and shoulders at 45450 and
34480 cm
-1
. These are also assigned to charge transfer transitions in tetrahedral environment
of
3
4
VO
. The minimum value of 10Dq for
3
4
VO
is expected at about 16000 cm
-1
in octahedral
geometry. This is expected because the two bands at 34480 and 45450 cm
-1
are from the
ligand orbitals to two vacant d orbitals which are 10Dq apart. This would be about twice the
energy separation (8000 cm
-1
) observed for tetrahedral
3
4
VO
.Hence the evidence does not
satisfy the assignment of bands to d-d transitions. Therefore the bands are due to charge
transfer transitions.
16. Chromium
Chromium is the 6
th
most abundant transition metal. Chromium is used in the
manufacture of stainless steel and alloys. The ground state electronic configuration is
[Ar] 3d
4
4s
2
. It exhibits +2 to +6 oxidation states. Most stable oxidation state are +2 (CrO),
+3 (Cr
2 O 3) and +6 (K 2 Cr 2 O 7).
16.1. Optical spectra
a. Divalent chromium(d
2
)
Cr
2+
has a d
4
configuration and forms high spin complexes only for crystal fields less than
2000 cm
-1
. The ground state term in an octahedral crystal field is
5
Eg belonging to the
31
2
gg
te
configuration. The excited state
5
T2g corresponds to promotion of one single electron to give
22
2
gg
te configuration. The d
4
electron is susceptible to Jahn-Teller distortion and hence Cr
2+
compounds usually are of low symmetry. In lower symmetry, the excited quintet state of
Cr
2+
splits into three levels and the ground level quintet state splits into two levels. In the
case of Cr
2+
(H2O)6, the value of Dq is 1400 cm
-1
. In spinels, Cr
2+
is in the tetrahedral
environment and Dq is about 667 cm
-1
only.
b.
Trivalent chromium(d
3
):
In octahedral symmetry, the three unpaired electrons are in
3
2
g
t orbitals which give rise to
4
A2g,
2
Eg,
2
T1g and
2
T2g states. Of these
4
A2g is the ground state. If one electron is excited, the
configuration is
21
2
gg
tewhich gives two quartet states
4
T1g and
4
T2g
and a number of doublet
states. When the next electron is also excited, the configuration is
12
2
g
g
tewhich gives rise to
one quartet state
4
T1g and some doublet states.
  
44 4 4
212
,,
ggg
FAFTFTF

44
1g
PTP
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
25
   
22 2 2 2
112
,,,
gggg
G AGTGTGEG
  
22 2 2
12
,2 ,
ggg
HEHTHTH
In both fields,
4
A2g,(F) represents the ground state. Hence, three spin allowed transitions are
observed in high spin state
4
A2g(F)
4
T2g(F) (1),
4
A2g(F)
4
T1g(F) (2) and
4
A2g(F)
4
T1g(P) (3).
These spin allowed bands split into two components when the symmetry of Cr
3+
ion is lowered
from octahedral to C
4V or C3V. Generally,
4
A2g(F)
4
T1g(P) occurs in the UV-Vis region.
The strong field electronic configurations for the ground state and their terms are given as
follows:

  
30
4222
22 12
:,,,
gg g g g g
te AFEGTGTG

 
21
442
2122
:,,
ggggg
t e TFTFTH


12
4
21
:
gg g
teTP
Racah parameter, B, is calculated with spin allowed transitions using equation (17)

22
12 12
21
23
15 27B


 (17)
The octahedral crystal field parameter Dq is characteristic of the metal ion and the ligands.
The Racah parameter, B depends on the size of the 3d orbital; B is inversely proportional to
covalency in the crystal.
16.2. EPR spectra of chromium compounds
Cr
3+
ion, splits into |1/2 and |3/2 Kramers’ doublets in the absence of magnetic field,
separated by 2D, D being the zero-field splitting parameter. This degeneracy can be lifted only
by an external magnetic field. In such a case, three resonances are observed corresponding to
the transitions, |-3/2 |-1/2, |-1/2 |1/2 and |1/2 |3/2 at gB – 2D, gB and gB +
2D respectively. In a powder spectrum, mainly the perpendicular component is visible. If all
the three transitions are observed, the separation between the extreme sets of lines is 4D [gB +
2D –(gB - 2D) = 4D]. If D is equal to zero, a single resonance line appears with g ~ 1.98. If D is
very large compared to microwave frequency, a single line is seen around g = 4.0.
16.3. Relation between EPR and optical absorption spectra
A comparison is made between the observed geff from EPR results and the calculated one
from the optical spectrum. For Cr
3+
, EPR and optical results are related by,
Advanced Aspects of Spectroscopy
26


11
4
1
8
e
g
gg
ET F

(18)


1
4
2
8
e
g
gg
ET F

(19)
Here g
11 and g
are the spectroscopic splitting factors parallel and perpendicular to the
magnetic field direction, g , the free electron value g
e, is 2.0023. These values give,

11 1
1
3
eff
g
gg
. (20)
The value of D can also be estimated from the optical absorption spectrum. The
4
A2g(F)
4
T2g(F)
component in the optical spectrum is due to the lowering of symmetry
which also includes the D term.

2
2
10
zx
D
Dq




. (21)
The spin-orbit splitting parameter, [for free ion, Cr
3+
is 92 cm
-1
]
is related to Racah
parameter (B) by the equation,
2
0.11 1.08 0.0062B

(22)
16.4. Typical examples
The data chosen from the literature are typical for each sample. The data should be
considered as representative only. For more complete information on specific examples, the
original references are to be consulted. X-band spectra and optical absorption spectra of the
powdered sample are recorded at room temperature (RT).
1.
Trivalent chromium [d
3
]: The optical absorption spectrum of fuchsite recorded in the
mull form at room temperature shows bands at 14925, 15070, 15715, 16400, 17730 and
21740 cm
-1
. The two broad bands at 16400 and 21740 cm
-1
are due to spin-allowed
transitions,
4
A2g(F)
4
T2g(F) and
4
T1g(F) respectively. The band at 17730 cm
-1
is the split
component of the
4
T2g(F) band. This indicates that the site symmetry of Cr
3+
is C4v or C3v.
The bands at 16400 and 21700 cm
-1
are responsible for the green color of the mineral.
The additional weak features observed for the
1 band at 15715 and 15070 cm
-1
are
attributed to the spin-forbidden transitions,
4
A2g
2
T1g(G) and
4
A2g
2
Eg(G). Using
equation (17), Racah parameter, B, is calculated (507 cm
-1
). Substituting Dq and B values
and using T-S diagrams for d
3
configuration and solving the cubic field energy matrices
,another Racah parameter, C is evaluated (2155 cm
-1
) which is less than the free ion
value [C =3850 cm
-1
].
Several examples are available in the literature. Some of them are given in the Table-12.
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
27
Compound
2
Eg(G)
cm
-1
2
T1g(G)
cm
-1
4
T2g(F)
(ν
1)
cm
-1
2
T2g(G)
cm
-1
4
T1g(F)
(ν2)
cm
-1
2
T1g(H)
cm
-1
4
T1g(P)
(ν3)
cm
-1
Dq
cm
-1
B
cm
-1
C
cm
-1
β
CFSE
Fuchsite
quartz
15500 15995 19995 22720 27020 35700 43465 2000 677 3400 0.66 24000
Dickite 14690 15500 16260 23800 37000 1626 803 0.78 19512
Fuchite 15070 15715
16400
17730
14925 21740 1640 507 2155 0.49 19680
Chromate 17390 23810 1739
Natural
Ruby
14262
14296
16725
16919
17042
18170
17245
21012
21058
21389
24993 1830 732 2155 0.71 21960
Variscite
16660
18180
15380 21735 30295 1666 475 2200 0.46 19992
Synthetic
Uvarovite
16670 18000 22730 28000
Sr3Ga2Ge4O14
Garnet
16299 433.6 1629.9 712.3 0.69 19559
Ureyite 15600 22000 664 0.65
Alexandrite 14000 - 16600 21000 25000
Uvarovite 16600 23100
Clinoclore 1834 668 0.728 63x350
Amesite 1782 737 0.899 58.0x
Muscovite 1610 737 0.89 55.6
Phlogopite 1690 58.0
1. The EPR spectrum of fuchsite recorded at room temperature (RT) clearly indicates a strong resonance line with a few
weak resonances on either side of it. The g value for this centrally located strong line is 1.98. This is due to the main
transition |-1/2 |1/2 of Cr
3+
. The calculated value of D is around 270 G. For weak lines, D is around 160 G. Since
the lines are equally spaced on either side of the strong resonance, E is zero. The strong line at g (1.98) value is
observed indicating a high concentration of chromium.
2. The EPR spectrum of chromate shows a broad EPR signal with g value of 1.903 which may be due to Cr
3+
which is in
high concentration in the mineral. The chromium ion is in octahedral coordination.
3. EPR spectrum of zoisite at LNT givesa g and D values of 1.99 and 42.5 mT respectively which are due to Cr
3+
in
octahedral environment.
4. EPR spectrum of chromium containing fuchsite quartz shows a g value of 1.996 which may due to Cr
3+
which is in
octahedral environment.
5. EPR spectrum of blue sapphire shows four Cr
3+
sites with the same g value of 1.98 having different D values
(130,105,65 and 34 mT) . Green sapphire also has the same g value but different D values (132,114, 94 and 35 mT). The
results suggest that chromium content is slightly different in different sapphires.
Table 12. Assignment of bands for Cr(III) with
4
A2g(F) ground state. All values are given in cm
-1
Several examples are given in the literature. Some of them are presented in the Table-13.
Compound
Observed
4
T1g(F)
(ν
2) cm
-1
4
T2g(F)
(ν
1) cm
-1
Calculated
g
g
11 geff geff (cm
-1
Varscite 1.958 1.9684 1.994 16660 21735 1.9615 75
Chromate 1.903
Table 13. EPR parameters of Cr
3+
compounds.
Advanced Aspects of Spectroscopy
28
2. Tetravalent chromium (d
2
):
Absorption spectra of Cr
4+
in forsterite and garnet show the absorption band at 9460 cm
-1
which
is the typical of Cr
4+
ions. It is attributed to the
3
A2g
3
T2g transition. The absorption
band at 19590 cm
-1
is also attributed to
3
A2g
3
T1g transition. The absorption band at 19590
cm
-1
overlaps with the bands at 16130 and 23065 cm
-1
.
17. Manganese
The atomic number of manganese is 25 and its outermost electronic configuration is [Ar]
3d
5
4s
2 .
It exhibits several oxidation states, +2, +3, +4, +6 and +7, of which the most stable are
+2 +4 and +7. The ionic radii of Mn
2+
and Mn
4+
are 0.80 and 0.54 A.U. respectively. Twenty
three isotopes and isomers are known. A number of minerals of manganese exists in nature
(~ 300 minerals) giving rise to an overall abundance of 0.106%. Twelve of the important
among them are economically exploited and the most important of these are pyrolusite
(MnO
2), manganite (Mn2O3.H2O), hausmannite (Mn3O4) rhodochrosite (MnCO3) and
manganese(ocean) nodules. Much of the (85-90%) manganese is consumed in the
manufacture of ferromanganese alloys. The other uses are: manganese coins, dry cell and
alkaline batteries and glass. It is an essential trace element for all forms of life.
Octahedral complexes of Mn(III) are prone to Jahn-Teller distortion. It is of interest,
therefore, to compare the structures of Cr(acac)
3 with Mn(acac)3 since the former is a regular
octahedron while the latter is prone to dynamic Jahn-Teller distortion.
17.1. EPR spectra of manganese compounds
1. Manganese(II): Manganese(II), being a d
5
ion, is very sensitive to distortions in the
presence of magnetic field. Mn(II) has a total spin, S = 5/2. The six spin states labeled as
±5/2>, ±3/2> and ±1/2> are known as the three Kramers’ doublets; in the absence of
external magnetic field ,they are separated by 4D and 2D respectively, where D is the
zero-field splitting parameter. These three doublets split into six energy levels by the
application of an external magnetic field. Transitions between these six energy levels
give rise to five resonance lines. Each of these resonance lines, in turn, splits into a
sextet due to the interaction of the electron spin with the nuclear spin of
55
Mn, which is
5/2. Thus one expects a 30- line pattern. However, depending on the relative
magnitudes of D and A (hyperfine coupling constant of manganese), these 30 lines
appear as a separate bunch of 30 lines or 6 lines (if D = 0). The separation between the
extreme set of resonance lines is approximately equal to 8D (first order). If D is very
small compared to hyperfine coupling constant (A), the 30 lines are so closely packed
that one could see only six lines corresponding -1/2 to +1/2 transition. If D = 0, the
system is perfectly octahedral. Deviation from axial symmetry leads to a term known as
E in the spin- Hamiltonian. The value of E can be easily calculated from single crystal
measurements. A non-zero value of E results in making the spectrum unsymmetrical
about the central sextet.
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
29
Further, the following parameters have been calculated from the powder spectrum using the
Spin- Hamiltonian of the form:

2
3
1
111
3
gz
HBSDSSS SA




(23)
Here the first term represents the electron-Zeeman interaction, the second term represents
the zero field contribution and the third term represents the nuclear-Zeeman interaction.
The extra set of resonances within the main sextet is due to the forbidden transitions. From
the forbidden doublet lines, the Zero field splitting parameter, D is calculated using the
formula,

2
2
116 8
2
964
m
mim
HAm
D
HHHA
H
m




(24)


2
0
22
2
0
or
8
35
1
4
2
o
mo m
HHAm H
II m A
A
HH
HAm m




(25)
where H
m is the magnetic field corresponding to m m in HF line; H0 is the resonance
magnetic field and m is the nuclear spin magnetic quantum number.
Percentage of covalency of Mn-ligand bond can be calculated in two ways using (i)
Matumura’s plot and (ii) electro negativities, X
p and Xq using the equation,

2
1
1 0.16 0.035
pq pq
CXXXX
n

(26)
Here n is the number of ligands around Mn(II) ion; X
p = XMn = 1.6 for Mn(II) and Xq = Xligand .
Also hyperfine constant is related to the covalency by,
41
2.04 104.5 10
iso
A
Ccm

(27)
Further, the g value for the hyperfine splitting is indicative of the nature of bonding. If the g
value shows a negative shift with respect to the free electron g value (2.0023), the bonding is
ionic and conversely, if the shift is positive, then the bonding is said to be more covalent in
nature.
17.2. Typical examples
1. Manganese(II): The EPR spectrum of clinohumite contains a strong sextet at the centre
corresponding to the electron spin transition +1/2> to -1/2>. In general, the powder
spectrum is characterized by a sextet, corresponding to this transition. The other four
transitions corresponding to ±5/2>
±3/2> and ±3/2> ±1/2> are not seen due to their
Advanced Aspects of Spectroscopy
30
high anisotropy in D. However, in a few cases only, all the transitions are seen. Moreover,
the low field transitions are more intense than the high field transitions. In addition, if E
0, the EPR spectrum will not be symmetrical about the central sextet. In clinohumite, the
spectrum indicates the presence of at least three types of Mn(II) impurities in the mineral.
The extra set of resonances within the main sextet is due to the forbidden transitions. From
the powder spectrum of the mineral, the following parameters are calculated:
Site I: g = 2.000(1), A = 9.15(2) mT; and D = 43.8(1) mT.
Site II: g = 2.003(2), A = 9.23(2) mT; and D = 44.1(1) mT.
Site III: g = 2.007(1), A = 9.40(2) mT; and D = 44.1(1) mT.
This large value of D indicates a considerable amount of distortion around the central
metal ion. Since EPR is highly sensitive to Mn(II) impurity, three such sites are noticed.
These two sites have close spin- Hamiltonian parameters. A close look at the EPR
spectrum indicates a non-zero value of E, which is very difficult to estimate from the
powder spectrum.
2.
Pelecypod shell EPR spectrum of powdered sample obtained at room temperature
indicates the presence of Mn(II) and Fe(III) impurities. The spectrum contains a strong
sextet at the centre of the spectrum corresponding to the electron spin transition +1/2>
to -1/2>. Also, the powder spectrum indicates the presence of, at least, three types of
Mn(II) impurities in the pelecypod shell which is noticed at the sixth hyperfine resonance
line. The third Mn(II) site is of very low intensity. The extra set of resonances within the
main sextet is due to the forbidden transitions. The variations of intensity are also due
to the zero field splitting parameter. From the powder spectrum of the compound, the
following parameters are calculated using the spin- Hamiltonian of the form:
2
1
3
Z
S
HBgSDSS SAI

(28)
where the symbols have their usual meaning.
Site I: g = 2.002(1), A = 9.33(2) mT; and D = 43.8(1) mT
Site II: g = 1.990(2), A = 9.41(2) mT; and D = 44.1(1) mT
Site III: g = 1.987(1), A = 9.49(2) mT; and D = 44.1(1) mT
This large value of D indicates a considerable amount of distortion around the central metal
ion. A close look at the EPR spectrum indicates a non-zero value for E.
The hyperfine constant ’A’ value provides a qualitative measure of the ionic nature of
bonding of Mn(II) ion. The percentage of covalency of Mn-ligand bond is calculated using
‘A’ (9.33 mT) value obtained from the EPR spectrum and with Matumura’s plot. It
corresponds to an ionicity of 94%. Also, the approximate value of hyperfine constant (A) is
calculated by using the equation (27).
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
31
The value obtained is 92x 10
-4
cm
-1
. This calculated value agrees well with the observed
hyperfine constant (93.3 x 10
-4
cm
-1
) indicating ionic character of Mn-O bond in the shell
under study.
Using the covalency, the number of ligands around Mn(II) ion is estimated using the
equation (26)

2
1
1 0.16 0.035
pq pq
CXXXX
n

Where X
P and Xq are the electronagativities of metal and ligand. Assuming Xp = XMn = 1.4 and
X
q = XO = 3.5, the number of ligands (n) obtained are 18. This suggests that Mn(II) may be
surrounded by eighteen oxygens of six
2
3
CO
ions.
i.
Manganese (IV): This ion in biological samples gives rise to EPR signal around 3.30.
ii.
(Mn
7+
ion also gives EPR resonance signal at about 2.45 in ceramic materials and in
biological samples.
17.3. Optical absorption studies
1. Manganese(II): The free ion levels of Mn
2+
are
6
S,
4
G,
4
P.
4
D and
4
F in the order of
increasing energy. The energy levels for Mn
2+
ion in an octahedral environment are
6
A1g(S),
4
T1g(G),
4
T2g(G),
4
Eg(G),
4
T1g(G)
4
A1g,
4
T2g(G),
4
Eg(D),
4
T1g(P) respectively with
increasing order of energy. The
4
Eg(G),
4
A1g and
4
Eg(D) levels are less affected when
compared to other levels by crystal field. Hence, sharp levels are expected relatively in
the absorption spectrum which is the criterion for assignment of levels of Mn(II) ion.
Since all the excited states of Mn(II) ion will be either be quartets or doublets, the optical
absorption spectra of Mn(II) ions will have only spin forbidden transitions. Therefore,
the intensity of transitions is weak.
Energy level diagram of Mn(II) is extremely complex. Exact solutions for the excited state
energy levels in terms of Dq, B and C may be obtained from T-S matrices. These matrices are
very large (up to 10 x10) and ordinary calculations are not feasible. For this reason, the T-S
diagrams given in many places in the literature are not sufficiently complete to allow the
assignment of all the observed bands. Therefore a set of computer programmes is written to
solve the T-S secular equations for any selected values of B, C and Dq. With the computer
program, it is only necessary to obtain values of B and C and the complete scheme for any
Dq can be quickly calculated. Fortunately B and C can be obtained analytically, if a
sufficiently complete spectrum is obtained using the transitions given below:
44 6
111
,105
gg g
AEG A BC

46
12
17 5
gg
ED A B C

Advanced Aspects of Spectroscopy
32
If ν1 and ν2 are correctly observed and identified in the spectrum, B and C can be calculated.
Identification is particularly easy in these cases because of the sharpness of the bands of
these levels and are independent of Dq.
2.
Manganese(III): This ion has four 3d electrons. The ground state electronic
configuration is
31
2gg
te. It gives a single spin-allowed transition
5
Eg
5
T2g corresponding
to one electron transition. This should appear around 20000 cm
-1
. Mn
3+
cation is subject
to Jahn-Teller distortion. The distortion decreases the symmetry of the coordination site
from octahedral to tetragonal (D
4h) or by further lowering the symmetry to rhombic
(C
2v). Under the tetragonal distortion, the t2g orbital splits into eg and b2g orbitals
whereas the e
g orbital splits into a1g and b1g orbitals. Hence in a tetragonal site, three
absorption bands are observed instead of one. Further distortion splits the e
g orbital into
singly degenerate a
1g and b1g orbitals. Thus four bands are observed for rhombic
symmetry (C
2v).
The transitions in the tetragonal field are described by the following equations:
22
11
:6 2 6 6 2 4 5
gg
B A Dq Ds Dt Dq Ds Dt Ds Dt



(29)
22
12
:4 2 6 2 10
gg
B B Dq Ds Dt Dq Ds Dt Dq


(30)
22
1
:4 4 6 2 10 3
gg
B E Dq Ds Dt Dq Ds Dt Dq Ds


(31)
In the above equations, Dq is octahedral crystal field and Ds and Dt are tetragonal field
parameters. The same sign of Dq and Dt indicates an axial elongation and opposite sign
indicates an axial compression.
The optical absorption bands observed for Mn(III) in octahedral coordination with rhombic
distortion (C
2h) in montmorillonite are given in Table -14.
Assignment Localities
D4h C2V (Mexico) (Gumwood Mine) (California)
5
B1g
5
A1g
5
B1g
5
B2g
5
B1g
5
Eg
5
B1g
5
A1g
5
B1g
5
A2g
5
B2g
5
B1g
5
A3g
10480
19041
20660
21837
10276
18751
20496
22127
10542
18560
20605
22143
Table 14. Assignment of bands for Mn(III) in montmorillonite
18. Iron
The atomic number of iron is 26 and its electronic configuration is [Ar]4s
2
3d
6.
. Iron has 14
isotopes. Among them, the mass of iron varies from 52 to 60 Pure iron is chemically reactive
and corrodes rapidly, especially in moist air or at elevated temperatures. Iron is vital to
plant and animal life. The ionic radius of Fe
2+
is 0.76 A.U. and that of Fe
3+
is 0.64 A.U. The
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
33
most common oxidation states of iron are +2 and +3. Iron(III) complexes are generally in
octahedral in shape, and a very few are in tetrahedral also.
18.1. EPR spectra of iron compounds
The EPR spectra of powdered Fe
3+
compounds may be described by the spin- Hamiltonian,


222
1
1
3
zXy
HgBSDS SS ES S




(32)
The second and third terms in the equation (33) represent the effects of axial and rhombic
components of the crystal field respectively. When D=E=0, it corresponds to a free ion in the
magnetic field, H and if E= 0, it implies a field of axial symmetry. If λ (E/D) increases, it
results in the variation of rhombic character. Maximum rhombic character is seen at a value
of λ=1/3 and further increase in λ from 1/3 to 1 results in the decrease of rhombic character.
When λ =1, the axial field situation is reached. When λ=1/3, the g value is around 4.27 and
when λ is less than 1/3, g value is 4. Hence, the resonance is no longer isotropic and the
powder spectrum in that region is a triplet corresponding to H along each of the three
principle axes. For Fe
3+
,
in fields of high anisotropy, the maximum g value is 9. If g values
are limited to 0.80 to 4.30, the Fe
3+
ion is under the influence of a strong tetragonal distortion.
1.
Iron (III): The iron (III) samples exhibit a series of g values ranging from 0 to 9. This is due
to the fact that the three Kramers’ doublets of S=5/2 are split into S5/2, S3/2 and
S1/2 separated by 4D and 2D respectively where D is the zero field splitting parameter.
Depending on the relative populations of these doublets, one observes g value ranging
from 0 to 9.0. The line widths are larger in low magnetic field when compared to high
magnetic field. If the lowest doublet, S1/2 is populated, it gives a g value of 2 to 6
whereas if the middle Kramers’ doublet S3/2 is populated, a g value 4.30 is expected. If
the third doublet S5/2 is populated, it gives a g value of 2/7 to 30/7. A few systems are
known which exhibit resonances from all the three Kramers’ doublets.
The iron(III) in the natural sample enters the lattice in various locations which may not
correspond to the lowest energy configuration. After heating the sample, the impurity
settles in the lowest energy configuration and the EPR spectrum is simplified. Thus, it is
observed that heating the sample results in a simplification of the EPR spectrum and gives a
g value of around 2.
18.2. Typical examples
1. The EPR spectrum of powdered red sandal wood obtained at room temperature
contains a series of lines of various intensity and width. The g values obtained for these
are 6.52, 2.63 and 1.92. These three peaks are attributed to Fe(III) impurity in the
compound.
2.
The EPR spectrum of prehnite at room temperature consists of two parts. The first part
consists of the two strong lines (absorption and dispersion) and the second part
Advanced Aspects of Spectroscopy
34
comprises a weak doublet within the strong doublet. The weak doublet also consists of
two lines, absorption and dispersion line shapes. The g values of the strong doublet are
4.48 and 3.78 whereas the g values of the weak doublet are 4.22 and 3.96. The data
reveal that there are two different centres of Fe(III) which are magnetically distinct.
3.
The EPR spectrum of nano iron oxalate recorded at room temperature reveals three sets
of four lines in low, medium and high fields corresponding to g
1, g2 and g3 respectively.
From the positions of the peaks in the EPR spectrum, the following spectroscopic
splitting factors are evaluated: g
1 = 2.130, g2 = 2.026 and g3 = 1.947. The hyperfine
structure constants are A
1 = 78 mT, A2 = 46 mT and A3 =26 mT. The EPR spectrum is
characteristic of Fe(III) ion or
2
HCO
or in rhombic symmetry. For the rhombic
symmetry, g values follow in the sequence as g
1 > g2 > g3. Using the relation, spin-orbit
coupling constant, λ is calculated. Resonant value of the magnetic field is given by the
relation,
21419.49 0.07144775
() ( )
()
R
HmT MHz
gcm g

(33)
λ calculated for each g tensor is 32.18.
For axial symmetry, λ is zero. If rhombic character in the crystal field is increased, it results
in the increase of λ upto a maximum of
1
3
. In the present case, the observed λ is
1
3
(32.18%).
Thus the EPR studies indicate that the iron oxalate nano-crystal is in orthorhombic structure.
18.3. Optical absorption spectra of iron compounds
18.3.1. Trivalent iron
Trivalent iron has the electronic configuration of 3d
5
which corresponds to a half-filled d -
sub-shell and is particularly most stable. In crystalline fields, the usual high spin
configuration is
32
2gg
te with one unpaired electron in each of the orbitals and the low spin
state has the
5
2g
t configuration with two pairs of paired electrons and one unpaired
electron. The energy level in the crystal field is characterized by the following features. i)
The ground state of d
5
ion,
6
S transforms into
6
A1g - a singlet state. It is not split by the
effect of crystal field and hence all the transitions are spin forbidden and are of less
intensity. ii) In excited state, d
5
ion gives rise to quartets (
4
G,
4
F,
4
D,
4
P) and doublets (
2
I,
2
H,
2
G,
2
F,
2
D,
2
P,
2
S) . The transitions from the ground to doublet state are forbidden because
the spin multiplicity changes by two and hence they are too weak. Thus sextet-quartet
forbidden transitions observed are:
6
A1g
4
T1g and
6
A1g
4
T2g. The transitions which are
independent of Dq and which result in sharp bands are
6
A1g
4
E(
4
D)
6
A1g
4
Eg+
4
E1g etc.,
iii) The unsplit ground state term behaves alike in both octahedral and tetrahedral
symmetries and gives rise to same energy level for octahedral, tetrahedral and cubic
coordination with usual difference,
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
35
:
48
1: :
9
:
9
Octa Tetra Cubic
Dq Dq Dq
18.3.2. Divalent iron
In divalent iron (d
6
), the free ion ground term is
5
D and the excited terms are triplet states
(
3
H,
3
P,
3
F,
3
G,
3
D) and singlet states (
1
I,
1
D). In an octahedral field, the
5
D term splits into an
upper
5
Eg level and a lower
5
T2g level of which the latter forms the ground state. The only
allowed transition is
5
T2g
5
Eg which gives an intense broad absorption band. This band
splits into two bands due to Jahn-Teller effect. The average of these two bands is to be taken
as 10Dq band. The transitions arising from the excited triplet states are spin forbidden and
hence are weaker than the 10Dq band.
18.3.3. Typical examples
1. For Fe
3+
, there are three transitions:
6
A1g(S)
4
T1g(G) (ν1),
6
A1g(S)
4
T2g(G)(ν2). ν1 occurs
between 10525 cm
-1
and ν2 occurs between 15380 to 18180 cm
-1
usually as a shoulder.
The bands corresponding to
6
A1g(S)
4
A1g(G),
4
Eg(G)
(ν3) appear around 22000 cm
-1
.
The last transition is field independent. The ligand field spectrum of ferric iron appears
as if the first (ν
1) and the third (ν3) bands of octahedral symmetry are only present. The
analysis of general features of the spectrum of Fe
3+
containing plumbojarosite is
discussed here. The first feature observed in the range 12000 to 15500 cm
-1
is attributed
to
6
A1g(S)
4
T1g(G), the third band at 22730 cm
-1
is sharp and is assigned to
6
A1g(S)
4
A1g(G),
4
Eg(G) transitions respectively. A broad and diffused band at 19045 cm
-1
is
assigned to the
6
A1g(S)
4
T2g(G) band. The other bands are also assigned to the
transitions with the help of Tanabe-Sugano diagram. The assignments are given in the
Table -15.
2.
Optical absorption spectrum of prehnite recorded in the mull form at room
temperature (RT) shows bands at 9660, 10715, 12100, 12610, 15270, 16445,17095, 23380
and 24390 cm
-1
in the UV –Vis region. For easy analysis of the spectrum, the bands are
divided into two sets as 12100, 15270, 23380 cm
-1
and 12610, 16445, 17095, 24390 cm
-1
.
Accordingly the two bands observed at 12100 cm
-1
in the first set and 12610 cm
-1
in the
second set are assigned to the same transition
6
A1g(S)
4
T1g(G) whereas 15270 cm
-1
in
the first set and 16445,17095 cm
-1
in the second set are assigned to
4
T2g(G) transition.
The third at 23380 cm
-1
and 24390cm
-1
is assigned to
4
A1g(G) ,
4
E(G) (3) transitions
respectively. These two sets of bands are characteristic of Fe(III) ion occupying two
different sites in octahedral symmetry. The broad and intense band observed at 10715
cm
-1
with a split component at 9660 cm
-1
is assigned to the transition
5
T2g
5
Eg for
divalent iron in the sample. Using the Tree’s polarization term, = 90 cm
-1
, the energy
matrices of the d
5
configuration are solved for various B, C and Dq values. The
evaluated parameters which give good fit are given in Table 15. A comparison is also
made between the calculated and observed energies of the bands and these are
presented in Table -15.
Advanced Aspects of Spectroscopy
36
Prehnite Plumbojarosite Transition
from
6
A1g
Site I Site II
Dq= 930, B= 600 and
C =2475 cm
-1
,α= 90 cm
-1
Dq= 900, B= 600 and
C =2500 cm
-1
α= 90 cm
-1
Dq= 900, B= 700 and C =2800
cm
-1
α= 90 cm
-1
Wave
length
(nm)
Wave number (cm
-1
)Wave
length
(nm)
Wave number (cm
-1
) Wave
length
(nm)
Wave number (cm
-1
)
Observed Calculated Observed Calculated Observed Calculated
827
655
430
12100
15270
23380
793
608
585
427
793
608
585
427
12610
16445
17095
24390
12528
16331
23276
800 650
525
440
410
385
330
265
240
12500
15385
19045
22730
24390
25975
30300
37735
41665
-- 15194
19379
22766
24815
26474
30656
37710
41125
4
T1g(G)
4
T2g(G)
4
A1g(G),
4
E(G)
4
T2g(D)
4
Eg(D)
Table 15. Band headed data with assignments for Fe(III) in various compounds
19. Nickel
Nickel is the 7
th
most abundant transition metal in the earth’s crust. The electronic
configuration of nickel is [Ar]4S
2
3d
8
. Nickel occurs in nature as oxide, silicate and sulphide.
The typical examples are garnierite and pentlandite. Nickel exhibits +1 to +4 oxidation
states. Among them divalent state is most stable. Nickel compounds are generally blue and
green in color and are often hydrated. Further, most nickel halides are yellow in color. The
primary use of nickel is in the preparation of stainless steel. Nickel is also used in the
coloring of glass to which it gives a green hue.
19.1. Electronic spectra of nickel compounds
The electronic distribution of Ni(II) ion (d
8
) is
62
2gg
te which gives rise to
3
F,
3
P,
1
D and
1
S terms
of which
3
F is the ground state. In a cubic crystal, these terms transform as follows:
33 3 3
12 2gg g
FTFTFAF
33
1g
FTP
13 1
2gg
DTDED
11 1 1 1
12 1ggg g
GTGTGEGAG
11
1g
SAS
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
37
Of these crystal field terms,
3
A2g(F) is the ground state. Hence three spin allowed transitions
are possible and the others are spin forbidden The three spin allowed transitions are:
3
A2g(F)
3
T1g(P),
3
A2g(F)
3
T1g(F) and
3
A2g(F)
3
T2g(F). These transitions are governed by linear
equations as given below:

1
33
2
21 1
15 7.5 6 1
gg
AF TP Dq B B

(34)
 
1
33
2
21 2
15 7.5 6 1
gg
AF TF Dq B B

(35)
33
22 3
10
gg
AF TF Dq

(36)
Here μ is of the order of 0.01. Dq and B are of similar magnitude. The spin allowed bands
are calculated using the above equations whereas the spin forbidden bands are assigned
using Tanabe-Sugano diagrams.
19.2. Typical examples
The data chosen from the literature are typical and representative for each sample. For more
complete information on any specific case, original references are to be consulted. X-band
spectra and optical absorption spectra of the powdered sample are recorded at room
temperature (RT) only.
Divalent Nickel [d
8
]: The optical absorption spectrum of falcondoite mineral recorded in the
mull form at room temperature shows three intense bands at 9255, 15380 and 27390 cm
-1
and
a weak band at 24385 cm
-1
. Using the equations 34 to 36, the calculated values of Dq and B
are 925 and 1000 cm
-1
respectively. Using these Dq and B values and T-S diagrams for d
8
configuration, the cubic field energy matrices and Racah parameter, C are evaluated (4.1B) .
Ni
2+
also gives absorption bands in the NIR region. These bands suggest that Ni
2+
is in
tetrahedral site. In some of the samples, Ni
2+
exbits both octahedral and tetrahedral coordination.
Several examples are available in the literature. Some of them are given in the Table-16.
Compound
3
T1g(P)
(ν1)
3
T1g(F)
(ν2)
3
T2g(F)
(ν3)
1
T1g(G)
1
T1g(D)
1
Eg(D)
1
T2g(D)
1
T2g(G) Dq B C
Falcondoite 27390 15380 9255 24385 925 1000 4100
Ullmannite 24993 14966 8618 25967 21546 12252 21546 860 840 3350
Takovite 26665 15380
8200
10000
14930 24095 910 940 4.25B
(Zn,Ni)KPO
46H2O
25967 15500 8770 14080 22216 900 890 3800
Ni(II) HZDT
Garnierite 26300 15200 9100 13000
Gaspeite 22730
13160
14705
7714
8685
20410 30300 810 800 3200
Annabergite 13885 8330
Zartite 23805 14285 8195 21735 820 899 4.1B
Table 16. Assignment of bands for Ni(II) with
3
A2g(F) as the ground state. All values are given in cm
-1
.
Advanced Aspects of Spectroscopy
38
19.3. EPR spectra
Ni
2+
(d
8
) has no unpaired electron (square planer) in its orbit. Therefore it does not exhibit
EPR signal at room temperature.
But in certain conditions, it shows EPR signal. The EPR data could be related with the
optical data by the following equation
8
2.0023g

where is the energy of the
transition of the perfect octahedral site. λ is 324 cm
-1
for free Ni
2+
ion.
20. Copper
Copper is one of the earliest known elements to man. The average percentage of copper in the
earth’s crust is 0.005%. Pure copper is soft and malleable. An important physical property of
copper is its color. Most people refer copper colour as reddish-brown tint. Copper-63 and
copper-65 are two naturally occurring isotopes of copper. Nine radioactive isotopes of copper
are also known. Among them two radioactive isotopes, copper-64 and copper-67 are used in
medicine. Copper easily reacts with oxygen and in moist air, it combines with water and
carbon dioxide forming hydroxy copper carbonate (Cu
2(OH)2CO3 ).
Animals like crustaceans (shellfish like lobsters, shrimps, and crabs) do not have
hemoglobin to carry oxygen through the blood but possess a compound called hemocyanin.
This is similar to hemoglobin but contains copper instead of iron. Copper is an essential
micronutrient for both plants and animals. A healthy human requires not more than about 2
mg of copper for every kg weight of the body. The main body parts where copper is found
in animals are the tissues, liver, muscle and bone.
20.1. Copper compounds
Copper exists in two ionic states, Cu(I) and Cu(II). The ionic radius of Cu(II) is 0.73 A.U. The
electronic configuration of Cu(I) is [Ar] 3d
10
and hence has no unpaired electron in its
outermost orbit. Hence it exhibits diamagnetism. The electronic configuration of Cu(II) is
[Ar]3d
9
and has one unpaired electron which is responsible for its para magnetism. The main
resources of copper are its minerals. Structural properties could be explored using electronic
and EPR spectra which provides information on bonding between ligands and metal ion.
20.2. Electronic spectra of copper compounds
In optical spectroscopy, transitions proceed between the split orbital levels whereas in EPR
spectroscopy they occur between spin sub- levels that arise due to the external magnetic
field. Thus EPR spectroscopy is a natural sequel to optical spectroscopy.
20.3. Optical spectra
In octahedral crystal field, the ground state electronic distribution of Cu
2+
is t2g
6
eg
3
which
yields
2
Eg term. The excited electronic state is t2g
5
eg
4
which corresponds to
2
T2g term. Thus
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
39
only one single electron transition, i.e.,
2
Eg
2
T2g, is expected in an octahedral crystal field.
The difference is 10Dq. Octahedral coordination is distorted either by elongation or
compression of octahedron leading to tetragonal symmetry.
Normally, the ground
2
Eg state is split due to Jahn-Teller effect and hence lowering of
symmetry is expected for Cu(II) ion. This state splits into
2
B1g(dx
2
-y
2
) and
2
A1g(dz
2
) states in
tetragonal symmetry and the excited term
2
T2g also splits into
2
B2g(dxy) and
2
Eg(dxz,dyz) levels.
In rhombic field,
2
Eg ground state is split into
2
A1g(dx
2
-y
2
) and
2
A2g(dz
2
) whereas
2
T2g splits into
2
B1g(dxy),
2
B2g(dxz) and
2
B3g(dyz) states. Thus, three bands are expected for tetragonal (C4v)
symmetry and four bands are expected for rhombic (D
2h) symmetry. Energy level diagram
of d-orbitals in tetragonal elongated environment is shown in Fig. 5.
The transitions in the tetragonal field are described by the following equations:
22
11
:6 2 6 6 2 4 5
gg
B A Dq Ds Dt Dq Ds Dt Ds Dt


(37)
22
12
:4 2 6 2 10
gg
B B Dq Ds Dt Dq Ds Dt Dq


(38)
22
1
:4 4 6 2 10 3 5
gg
B E Dq Ds Dt Dq Ds Dt Dq Ds Dt


(39)
In the above equations, Dq is octahedral, Ds and Dt are tetragonal crystalfield parameters.
The same sign of Dq and Dt indicates an axial elongation [Fig. 5] and opposite sign indicates
an axial compression .
Figure 5. (a) Energy level diagram of Jahn-Teller distortion in d-orbital in octahedral and tetragonal
elongation
The Jahn-Teller distortion is either tetragonal elongation along the Z axis or contraction in
the equatorial xy plane which may ultimately result in a square planar environment in
extreme cases as in D
4h.
The optical absorption bands observed for Cu(II) in octahedral coordination with rhombic
(D
2h) symmetry are:
2
A1g(dx
2
-y
2
)
2
A2g(dz
2
),
2
A1g(dx
2
-y
2
)
2
B1g(dxy),
2
A1g(dx
2
-y
2
)
2
B2g(dxz),
2
A1g(dx
2
-y
2
)
2
B3g(dyz) states respectively. This is shown in Fig.6. In rhombic (D2h) field, i.e.,
C
2V symmetry, the strong band
2
A1g(dx
2
-y
2
)
2
B1g(dxy) gives 10Dq value which depends on
the nature of the compound.
Advanced Aspects of Spectroscopy
40
Figure 6. Energy level diagram of d-orbitals in rhombic distortion.
20.4. EPR spectra of copper compounds
When any Cu(II) compound in the form of powder is placed in a magnetic field, it gives a
resonance signal. The signal is of three types. They are shown in Fig.-7:
Figure 7. Different forms EPR spectra of Cu(II)
Fig.7(i) is due to high concentration of copper; if the copper content in the compound is high, it
gives a broad resonance line. Therefore the hyperfine line from either
63
Cu or
65
Cu cannot be
resolved. The g value for this resonance is around 2.2. (ii) Compression in the equatorial plane
results in the elongation of Z axis .Elongation in the equatorial plane results in the compression
of Z-axis. Thus there are two types of possibilities in the EPR spectrum. Hence an EPR
spectrum similar to Fig. 7(ii) & (iii) is obtained. If g
11 >g
, the ground state is
2
B1g, [Fig. 7(a)]
whereas if g
>g11 or g11 = 2.00, the ground state is
2
A1g [fig.7(ii).]. The highest-energy of the
half occupied orbital is d
x _
2
y
2
as it has the largest repulsive interaction with the ligands in the
equatorial plane. Here g
11(corresponding to the magnetic field oriented along the z axis of the
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
41
complex) > g
> 2.00. This is a characteristic feature of dx
2
-y
2
ground state. Additionally, copper
has a nuclear spin of (I)) 3/2 which couples with the electron spin to produce a four line
hyperfine splitting of the EPR spectrum. This is shown in Fig-7(ii) and 7(v). Tetragonal cupric
complexes generally have large A
11 value than those of complexes with D4h symmetry. If g11 >
g
, the ground state is
2
B1g whereas if g
>g11 or g11 = 2.00, the ground state is
2
A1g. EPR results
give rise to a new parameter, G which is defined as

11 e
e
g
g
G
g
g
(40)
If G value falls in between 3 and 5, the unit cell contains magnetically equivalent ions. If G
value is less than 3, the exchange coupling among the magnetically non- equivalent Cu(II)
ions in the unit cell is not very strong. If G is greater than 5, a strong exchange coupling
takes place among the magnetically non -equivalent Cu(II) ions in the unit cell. Truly
compressed structures are relatively rare when compared to elongated structures. In other
words, g
> g11, is an unusual observation and this implies two possibilities:
i.
The concentration of copper in the complex is very high which results in the interaction
between Cu(II)
Cu(II) ions.
ii.
The Cu(II) ion is a compressed octahedron. If the complex contains low copper content, it is
assumed that Cu(II) ion is a compressed octahedron. Hence the ground state is
2
A1g
2
()
z
d
.
iii.
Further lowering of symmetry gives rise to EPR spectrum which is similar to the one
shown in Fig. 9(iv). This spectrum consists of three sets of resolved four lines in low,
medium and high fields corresponding to g
1, g2 and g3 respectively. The hyperfine
structure constants (A values) are designated as A
1, A2 and A3 respectively. Line width
is estimated for simple cubic lattice using dipole-dipole equation;
2.3 1
pO
Hgss

(41)
where β is the Bohr magneton, s = spin, g
O = average value of g factor, ρ = density (2.22 x 10
21
spins/cc).
The calculated g values provide valuable information on the electronic ground state of the ion.
If g
1> g2 > g3, the quantity R value is given by (g2 –g3) / (g1-g2) which is greater than unity and
the ground state is
2
A2g(dz
2
); if it is less than unity, the ground state is
2
A1g(dx
2
-y
2
). A large value
of g
1 is indicative of more ionic bonding between metal and ligand. Further the structure of the
compound is an elongated rhombus. From the spin –Hamiltonian parameters, the dipolar
term (P) and the Fermi contact term (k) are calculated using the following expressions:
3
2
Cu O N
Pr

(42)
O
e
A
kg
P




(43)
Advanced Aspects of Spectroscopy
42
Here γCu is the magnetic moment of copper, βo is the Bohr magneton, βN is the nuclear
magneton and r is the distance from the central nucleus to the electron, A
o is the average A
value and g
o = go – ge where go is the average g value and ge is the free electron g-value
(2.0023). The Fermi contact term, k, is a measure of the polarization produced by the uneven
distribution of d-electron density on the inner core s-electron and P is the dipolar term. By
assuming either the value of P or k, the other is calculated. Using these values, the hyperfine
constant is calculated. This is the average value of g
1, g2 and g3.
Using the data of EPR and dipolar term P, the covalency parameter (α
2
) is calculated .

2
31
132
7116
61414
eee
AA
g
ggggg
P




(44)
Thus the important bonding information is obtained. The bonding parameter, α
2
, would be
closer to unity for ionic bonding and it decreases with increasing covalency. Further the
term,
k, is calculated using the EPR data,
22
11 11
43
77
Ak P g g


(45)
22
211
714
Ak P g



(46)
20.5. Relation between EPR and optical absorption spectra
The optical absorption and EPR data are related as follows. In tetragonal symmetry, EPR
studies are correlated with optical data to obtain the orbital reduction parameter in rhombic
compression.
22
1
1
8
e
xy
ak
gg
E

(47)
2
2
2
1
23
e
xz
ka b
gg
E

(48)
2
2
3
1
23
e
yz
ka b
gg
E

(49)
Similarly for rhombic elongation,
22
1
1
8
e
xy
ak
gg
E

(50)
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
43

2
2
2
1
23
e
xz
ka b
gg
E

(51)

2
2
3
1
23
e
yz
kab
gg
E

(52)
where cosa
and sinb
which are coefficients for the mixing of the z
2
and x
2
-y
2
orbitals. a
2
+b
2
= 1 and k1, k2, k3 are the orbital reduction parameters. λ is the spin- orbit
coupling constant for free Cu(II) ion = -830 cm
-1
.
In equations (48) to (50), when a = 0, tetragonal compression is obtained [ground state is
2
A1g(dz
2
)].
11
2.0023
e
g
g
(53)


22
1
,
6
e
xy yz
gg
EBE


(54)
Also in equations (51) to (53), when b is equal to zero, tetragonal elongation is obtained
[ground state is
2
B1g(dx
2
-y
2
)].


11
22
1211
11
8
e
xy
gg
EBB


(55)


22
1
,
2
e
xy yz
gg
EBE


(56)
Further, if A11, g11 and g
values are known, α
2
can be estimated using the equation [53]

2
11
11 1
3
0.04
0.036 7
ee
A
gg gg




(57)
20.6. Typical examples
EPR and optical absorption spectral data of selected samples are discussed. The data are
chosen from the literature for each typical sample. However, it is to be noticed that the
crystal field parameters, EPR parameters often depend on chemical composition, nature of
ligands and temperature of the compound. The data should be considered as representative
only. For more complete information on specific example, the original references are to be
consulted. The X-band spectra and optical absorption spectra of powdered samples are
mostly recorded at room temperature (RT).
Advanced Aspects of Spectroscopy
44
1. The EPR spectrum of covellite is shown in Fig-9. It is similar to the Fig 8(i). It consists of
a broad line with a small sextet. The g value for the broad line is 2.24 which is due to the
presence of Cu(II) in the sample. The hyperfine line from either
63
Cu or
65
Cu could not
be resolved since the copper content (Cu = 66 wt%) in the mineral is very high. Several
copper compounds exhibit this type of EPR spectra.
Figure 8. EPR spectrum of covellite at RT
Figure 9. EPR spectrum of beaverite at RT
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
45
2. Beaverite [Pb(Fe
3+
,Cu,Al)3(SO4)2(OH)6]: X-band EPR spectrum of powdered sample
recorded at RT is shown in Fig-9. This is similar to Fig-7(ii). The g values are:
g11 =
2.42 and
g
= 2.097. In addition to the above, a g value of 2.017 is observed which is
due to Fe(III) impurity. Fig.9 indicates expanded form of EPR spectrum of Cu(II) and
is not resolved because of high copper percentage. Tetragonal cupric complexes with
D
4h symmetry, possessing axial elongation have ground state
2
B1g (dx
2
y
2
).The EPR
results are in the order of
g11 > g
> ge and hence the ground state is
2
B1g. Though the
optical absorption spectrum shows two sites for Cu(II) with same ground state, the
same is not noticed in the EPR spectrum because the percentage of copper is high in
the sample.
A typical EPR spectrum of enargite is shown in Fig.10. The spectrum is symmetric
with
g11 = 2.289 and g
= 2.048 which are due to Cu(II). Since g11 > g
> ge, the ground
state for Cu(II) is
2
B1g (dx
2
y
2
). Using EPR and optical absorption results, the orbital
reduction parameters are evaluated, i.e., K
11 = 1.03 cm
-1
and K
= 1.93 cm
-1
. Also G
seems to be 5.0 which indicates that the unit cell of the compound contains
magnetically equivalent ions.
Figure 10. EPR spectrum of enargite at RT
Advanced Aspects of Spectroscopy
46
Figure 11. EPR spectrum of CuO-ZnO nano composite.
CuO-ZnO nano composite: EPR spectrum of CuO-ZnO nano composite recorded at room
temperature is shown in Fig-11. The calculated g values are 1.76, 2.31 and 2.05. The g
value of 1.76 is assigned to free radical of O
2-
. Further gII value of 2.31, g
value of 2.05
are due to Cu(II) in tetragonal distortion. Also it has A11 =13.3 mT. These results show
that the ground state of Cu(II) as d
x
2
- y
2
. Further, the covalency parameter, α
2
(0.74)
suggests that the composite has some covalent character.
3.
Atacamite [Cu2(OH)3Cl]: The EPR spectrum is shown in Fig.12. The g values
corresponding to three sets of the resolved four lines in low, mid and high fields are
g
1 = 2.191, g2 =2.010 and g3 = 1.92. The corresponding hyperfine structure constants are
A
1 = 11.0 mT, A2 = 3,0 mT and A3 = 5.0 mT respectively. Since g1 > g2 > g3, the quantity
R = (g
2 –g3)/(g1-g2) = 0.50 which is less than unity. This indicates
2
A1g(dx
2
-y
2
) is the ground
state for Cu(II) which is in an elongated rhombic field. The optical absorption spectrum
of the compound at RT shown in Fig-13 shows bands at 15380, 11083, 10296 and 8049
cm
-1
. Using the EPR results, the energy states are ordered as
2
A1g(dx
2
-y
2
) <
2
A2g(dz
2
) <
2
B1g(dxy) <
2
B2g(dxz) <
2
B2g(dyz). Thus we have four bands with
2
A1g(dx
2
-y
2
) as the ground
state. Using the EPR results, the dipolar term (P) and the Fermi contact term (k) are
calculated as 0.38 cm
-1
and k = 0.3 respectively. The bonding parameter, α
2
is found to be
0.28 indicating reasonably high degree of covalent bonding between metal and ligands.
Synthetic copper doped
zinc potassium phosphate hexahydrate (ZPPH), ZnKPO4 6H2O: It is
similar to strubite, a bio-mineral. The g values are: g
1 = 2.372, g2 =2.188 and g3 = 2.032.
The hyperfine structure constants are A
1 = 78 x 10
-4
cm
-1
, A2 = 48 x 10
-4
cm
-1
and A3 = 63 x
10
-4
cm
-1
respectively. It is seen that g1 > g2 > g3 and the quantity R = (g2 –g3)/(g1-g2) = 0.85.
This confirms that the ground state for Cu(II) is
2
A1g(dx
2
-y
2
) ( elongated rhombic field ).
Using the EPR data and substituting free ion dipolar term [P= 0.036 cm
-1
] for Cu(II) and
g
e value in equation (57), the bonding parameter, α
2
= 0.55, is obtained. It indicates a
predominant covalency in compound.
Electronic (Absorption) Spectra of 3d Transition Metal Complexes
47
Figure 12. EPR spectrum of atacamite at RT
Figure 13. Optical absorption spectrum of atacamite
Author details
S.Lakshmi Reddy
Dept. of Physics, S.V.D.College, Kadapa, India
Tamio Endo
Dept. of Electrical and Electronics Engineering,
Graduate School of Engineering, Mie University, Mie, Japan
G. Siva Reddy
Dept. of Chemistry, Sri Venkateswara University, Tirupati, India
Advanced Aspects of Spectroscopy
48
21. References
[1] B.N.Figgs,M.A.Hitchman, ”Ligand Field Theory and Its Applications”,Wiley-VCH,
New York,(2000).
[2]
A.Lund, M.Shiotani, S.Shimada,“Principles and Applications of ESR Spectroscopy”,
Springer New York (2011).
[3]
C.J.Ballahausen, “Introduction to Ligand Field Theory”, Mc Graw-Hill Book Co., New
York (1962).
[4]
P.B. Ayscough,”Electron Spin Resonance in Chemistry”, Mathuen & Co., Ltd., London
(1967).
[5]
R.L.Carlin, “Transition Metal Chemistry”, Marcel Dekker,New York (1969).
[6]
Journal of “Coordination Chemistry Reviews”.
[7]
Journal of Spectrochimica Acta A Elsvier.
[8]
J.S.Griffith, “Theory of Transition Metal Ions”, Cambridge University Press,Oxford
(1964).
[9]
Journal of Solid State Communications.