CHAPTER 6 PART 1 SPECTROSCOPIC PROPERTIES OF

TRANSITION

OBJECTIVES
In this Chapter , we shall learn how to interpret the spectrscopic properties of ccomponds
of transition elements . To do so, we make use of the Principles learnt in Chapter 5.

INTRODUCTION . In Chapter 5 , we discussed how crystal Fields of

various symmetries split the various d-orbitals into low energy and high energy
components. We saw how electrons are logically distributed in these orbitals. And,
depending on whether the fields are strong or weak, electrons may be paired or occupy
the orbitals singly. How does this information help us explain the origin of colour in
transition metal compounds?
SPECTRAL PROPERTIES OF TRANSITION METAL COMPLEXES
When a co-ordination complex absorbs radiation, electrons within various orbitals are
rearranged to high energy configurations. When the electrons revert to the low energy
rearrangement, energy is given off and may be seen if in the visible region (400-700nm).
For this course, we shall confine ourselves to electron rearrangements within the d-
orbitals. Let us use as an example, an aqueous solution of titanium(III) which we know
contains the species [Ti(H2O)6]3+ . Before absorbing any radiation, the electron
arrangement in this ion is , [Ar](t2g)1 ( Figure6.1a) .

[Ar](t2g)1 Absorption of radiation [Ar](eg)1

Ground state Excited state
The ion does not, however, stay in this excited state all the time. Hence, this electron
moves back to the low energy orbital of type t2g(Figure 6.1a) and in the process, energy is
given off.

[Ar](eg)1 [Ar](t2g)1 ,
Excited State Energy given off Ground State
 eg-set
eg-set

d1

t2g-set
d1
Figure 6.1a ..Electron arrangement in
a d1ion eg [Ti(H2O)6]3+inan octahedral t2g-set
field before absorbing energy Figure 6.1b..Electron arrangement in
(Ground state) a d1ion eg [Ti(H2O)6]3+inan octahedral
field after absorbing energy
(Excited state)
.

The energy is released when an ion moves from an excited state to a lower energy state.
This energy gives the colour observed. Eg , a UV-VIS spectrum of TiCl 3.6H2O has a
strong absorption peak around 20,000cm-1, attributed to the electronic transition,

[Ar](eg)1 [Ar](t2g)1 ,
Excited State Energy given off Ground State

That is, the ion moves from the excited state ( Figure 6.1b) to the ground sate (Figure
6.1a)

19,900 cm - Increasing Energy

Figure 6.2 – UV-VIBLE Spectrum of TiCl3.6H2O
Note Whereas an arrow gives the impression that an electron is jumping from one spot to
another , the concept is miss leading. Rather, what is actually happening is that the
electrons could be rearranged while at the same spot. It is therefore, recommended that
henceforth, we view electronic transitions as electronic rearrangements , A
rearrangement from low energy arrangement to a higher energy arrangement takes place
when energy is absorbed. A rearrangement from high energy to a lower energy one
results in emission of energy This is actually the origin of colour in transition metal
compounds.

ORIGIN OF COLOUR IN IONS WITH MANY ELECTRONS.

The origin of colour in complexes of ions such as Ti 3+ is fairly simple to explain

since one is dealing with movement of just one electron . However, for many- electron
ions, the problem is more challenging. Fortunately, the principles are exactly the same
,namely, “an electronic arrangement from a low energy arrangement to a high energy
arrangement is accompanied by absorption of energy” and an electronic arrangement
from high energy to one of low energy is accompanied by release of energy”. Either of
these electron rearrangements is called an “electronic transition”. Thus, an electronic
transition is not necessarily a movement of electrons from one position to another.
Rather, it is just a rearrangement .
An electron in an atom or ion is fully described by four quantum numbers. These are:-
(i) The principal quantum n . This indicates the shell the electron is in.
(ii) The azimuthal quantum number, l which indicates the type of orbital (s, p, d, etc) the
electron is in .
(iii) The magnetic quantum , ml.
(iv) The spin quantum , ms.
Here, ml and ms refer to the components of l and the spin s along the direction of
quantization ( z-axis) . When all the four quantum numbers for a particular electron are
known, then we say that we know the microstate of that electron.
Pauli’s Exclusion Principle. This states that no two electrons in the same atom or ion
can have a set of all the four quantum numbers being identical. Three quantum numbers
can be identical but then the fourth quantum numbers must differ.To illustrate this , we
shall use the two electrons in a 3d2 ion such Ti3+ or V3+. Here, two of the four quantum
numbers are already fixed for each of the two electrons. The reason is that d-orbitals are
populated only when principal quantum number n is 3 or higher . Furthermore, for an
electron in a d-orbital, l must be 2 .Thus for each of the electrons, n = 3 and the so-called
azimuthal quantum number l =2 .The l value indicates the type of orbital the electron is
in.
Let the Arabic numerals 1 and 2 written as left subscripts against n, l, ml or ms signify
whether one is referring to first or second electron . A plus sign, + , or a minus sign, - ,
used as a right superscript on the ml signifies whether the ms value is +½ or - ½ . For
example , for the two electrons in a 3d2 ion, the following quantum numbers are already
fixed.
n1=n2=3 ; l1=l2=2 .The ml , values range from +l to –l . Thus, in the present case, the l
values range between +2 and -2 i.e 2,1,0,-1, -2.The ms values are either +½ or - ½ .
With these definitions, we can confidently say that , the electron arrangement (2 +, 2- ) , is
a microstate since it does not violate Pauli’s
Exclusion principle. The other possible microstates for a d 2 ion are summarized in table
6.1a(2)

We note that since the table repeats itself for negative values of M L, only
microstates for positive values of ML, =0,1,2,3,4 have been shown. When we take into
account even those microstates for negative M L, we note that for a 3d2 ion, there are 45
microstates . This is true even for 4d2, 5d2 or 3d2 ions.

Table 6.1a MICROSTATES ARISING FROM an nd2 ion.

MS
ML 1 0 -1
4 (2+, 2-)

- +
(2+, 1-) (2 , 1 ) (2-, 1-)
3 (2+, 1+)

- +
(2+, 1-) (2 , 1 ) (2-, 1-)
2 (2+, 0+)
(1+, 1-)

(1+,0+) (2+,-1+) (1+,0-)(I-, 0+) (1-,0-) (2-,-1-)

1 (2+,-1-) (2-,-1+)

(2+,-1-) (2-,-1+) (2+,-1+) (1-,-1-)

0 (2+,-1+) (1+,-1+)
+ - - +
(1 ,-1 ) (1 ,-1 )
(0+,0-)

PICKING VARIOUS TERMS FROM A COLLECTION OF

MICROSTATES .
At this stage, one may naturally ask the question, “Do all the forty five microstates
calculated for a d2 ion have different energies? The answer is that,there several
groupings of microstates , each group with same energy .At this juncture , we note that a
collection of several microstates with the same energy is called a TERM.
In the case of a d2 ion, there is group of nine microstates , labelled the 1G Term, with
the same energy.. There is another group of twenty one microstates , labelled the 3F
Term, with the same energy. How are these microstates picked from a collection of so
many microstates ?
THE PROCESS OF PICKING TERMS . The procedure for picking microstates
which constitute a term is illustrated using as nd2 ion and is as follows
1: We re-draw Table 6.1a and label it as Table 6.1b.
2 We move to the top row in the box on first row and first column and proceed as
follows:-
(i)We move along the row from left to the right and, when we come across a microstate,
we pause . We mark this microstate with a sign that will help us avoid double counting.
In the present case, the only microstate on this row is (2+,2-) and is in the column with
MS=0. We put a single star as a left superscript so that the microstate now becomes,
(2+,2-)*.It should be noted here that one can choose any other symbol .
(ii) We now move down this column marking only one microstate from each box
with this star regardless of what the ml and ms values are. When we take into account
both positive and negative values of ML on this column, it is clear that there are 9
microstates . Nine microstates from this column have same energy and constitute a
TERM.

TERM LABEL,TERM MULTIPLICITY AND TERM DEGENERACY.

A Term is given a label that shows the ML value and the spin multiplicity .
. Thus, just as a value of l=o shows an s-orbital( sometimes labeled a, or b orbitals) ,
ML=0 shows an S=Term (sometimes labeled A1 orA2 ). Similarly, just as
a value of l=1 signifies a p-orbital, ML=1 signifies a P-Term
As a value of l=2 signifies a d-orbital, ML=2 signifies a D-Term
As a value of l=3 signifies a t- set of orbitals, ML=3 signifies a T-Term
As a value of l=4 signifies a g-orbital, ML=4 signifies a G-Term etc
Spin Multiplicity of A TERM . This is given by the formula, (2ML+1) and is written
as a left superscript against the term label. In this configuration there are nine microstates
with same energy and we say that they constitute a term, 1G term .
The multiplicity of a term X is written as the left superscript (2M L+1) .i,e the term X
with multiplicity (2MS+1) is written as , (2MS+1) X.
Note that , just as small letters a,b, e, h, f ,t, g,, represent orbitals, capital letters
represent Terms(ie.Energy Levels) .The collection of the nine microstates, therefore,
represents a G Term. From the relation, (2MS+1) X, this is a singlet G Term written as ,1G.
Reason: 2MS+1=2x0+1=1

OTHER TERMS.
There is no other microstate on this row of M L=4. So, we move to the row where
ML =3 and again, move to the box on left column where M S=1.
There is only one microstate on this box namely, the microstate labelled (2 +,1+) . We
mark this microstate with two stars , again, for the purpose of avoiding double counting
so that the microstate now becomes, (2+,1+)**. We move down this column picking one
microstate from each box and marking it with the double star sign, again , regardless of
what ml and ms values are . We count a total of seven microstates in this column.. Next,
we move back to the row of ML=3, where there is the microstate, (2+,1+)** in Figure
2.1b and move along the row to the column of M S=0.) , we find two unmarked
microstates. We pick the one (2-,1+) and mark it with two stars to become (2-,1+)**
(see Figure 6.1b) . As before, we move down this column picking one microstate from
each box. On this column, we also pick seven microstates .
We move back to the row of ML=3 and MS=0 and continue our journey to the right
and on column of MS=-1 ,we find the microstate (2-,1-) . We mark it with the double star
to become, (2-,1-)**. We move down this column marking one microstate from each box
with this double star and find that we have another seven microstates . So, in total, we
have 21microstates marked with double star. These 21 microstates constitute an 3F-
Term.
Next, we move to the row of ML=2 and repeat the procedure. Here, we find that there
is no unmarked microstate on the first column. Hence, we move to the column of M S=O
and find an unmarked microstate , (1+,1-) which we mark with tripple star to become
(1+,1-)***. We move down this column picking one unmarked microstate from each box
and marking with the triple star. In all, we pick five microstates. These five microstates
constitute a 1D Term.
Next, we move to the column of ML=1. On the box of ML=1 and MS=1, there is an
unmarked microstate (1+,0+) which we mark with four stars to become, (1+,0+)****.We
repeat the process of marking microstates the way we did for M L=3 values and find that
we have a total of 9 such microstates. These 9 microstates constitute a 3P Term.
Finally, we note one unmarked microstate on the M L=0,MS=0 box. This single
microstate is a 1S-Term.

Table 6.1b MICROSTATES ARISING FROM an nd2 ion.

ML
MS
1 0 -1
(2 , 2 ) *
4
+ -

(2+,*1-) (2 , 1 *)*
- +
(2-, 1-)**
3 (2+, 1+)**

(2+, 0+* *(2+, 1-) (2-, 1+*) (2-, 1-*)*

2 )*
(1+, 1-)**
*
*

(1+,0*+*
)* * (2+,-1+*
)* (1+*,0-)(I-, 0+*)* (1*-,0
* -) **
(2-,-1-)* *
(2+,-1-) (2-,-1*+*)
*
1

**** * -) (2-,-1*+*) (2+*,-1

***
* +) (1-*,-1-)
(2+,-1
(2+,-1*
+*

0
(1+,-1+)
)
(1+*
*
**-) (1-,-1
,-1 * *+*)
(0+,0-)

LABEL
We have worked systematically and shown that , a nd 2 ion has the following Terms.
3
F, P, 1G, 1D and 1S.
3

ACHIEVEMENT. The above exercise has helped us to put the 45 microstates into
clusters of
9 microstates of same energy constituting 1G TERM .
21 microstates of same energy constituting 3F TERM
5 microstates of same energy constituting 1D TERM .
9 microstates of same energy constituting 3P TERM .
1 microstate of same energy constituting 1S TERM .

Exercise . 1Work out the microstates arising from a np2

ion .
MICROSTATES FOR IOONS WITH LARGE SHELL CAPACITIES.

If you have honestly worked out the microstates for a d2 ion( the result is valid for any
nd2 ion , n=3,4,5,6,)., you will obviously have noted that the exercise is rather tedious!
The procedure is, however, very important for two reasons:-
(i) It helps us see at a glance the type of terms that arise from a configuration
(ii) It helps us pick lowest energy term. otherwise called, Ground state Term).
There are some simplificanteresting

(a) GROUND STATE TERM .

Another question of interest is:- Which of these terms , is the lowest energy, or, as we
call it, Ground State Term)? The Lowest energy term is deduced from Hund’s Rules.
These rule state:
(i) That term with highest spin multiplicity is the Ground State Term.
(ii) If there are two or more Terms with the highest spin multiplicity, the term with
highest ML value is the ground state term. For a d2 ion( and d8), two Terms, 3F and 3P
have the highest spin multiplicity. The 3F has an ML value of 3 while the 3P has ML
value of 1. We, therefore, conclude that the 3F term is the ground state term.
Hole-Formalism. Deducing No of Microstates for other configurations
No doubt, you have noted that , working out the 45 microstates in a nd 2 ion is
rather time-consuming . Working out those for a d 3 ion is even more time-consuming .
This has a total of 120 microstates. Working out number of microstates in d 4 ion from
first principles is even more tedious. This has a total of 210 microstates .A d 5 has atotal
of 252 microstates . An f3 ion has a total of 338microstates.. A logical question here is:-
Is there an alternative way of getting microstates especially for those configurations with
higher electron capacities such as the f-orbitals? .The answer is that , “There is”. We
make use of a principle called, the Hole Formalism .
According to this principle, if an orbital has capacity for N electrons but it is
populated only by n electrons, then , the number of microstates in an ion with (N-n)
electrons is the same as that for an ion with n-electrons. This implies that:-
Number of microstates in a p2 ion is the same as that for p4 ion. And, by extension, the
number of microstates in a d2 ion is the same as that for a d8 ion. . When considering the
terms, we note that number of terms in d2-ion, is the same as number of terms in a d8 ion
This means that, once we have worked out carefully the number of microstates and terms
in a d2 ion, we can readily deduce those for a d 8 ion.
Formula for calculating number of possible microstates.
The number of microstates, Nm, that are possible for given configuration can also be
computed from the formula

Nm, = ( N!) / (N-n)!n! where N=the maximum sub-shell capacity; and n= number of
electrons present.
For example, for d2 ion, we have painfully calculated a total of 45 microstates!
By using this formula, same information can be got in a matter of a few seconds.
Thus, using the above formula,
number of microstates Nm, = ( N!) / (N-n)!n!
where N=the maximum sub-shell capacity=10 for d-orbitals.
Here, number of electrons present=2.
Substituting, Nm=(N!/(N-n)!n! =10!/8!x2!
= 10x9x8!/8!x2! =45 .
CAUTION!! While working from first principles is rather tedious, it has the advantage
that , one can pick the microstates arising from a configuration and know types of terms
and their multiplicities. The use of the formula does not give any of this information

THE FREE ION TERMS on left margins of Figures 6.3a and 6.3b). The difference
comes in only when these ions are put in crystal fields. For a d 2 ion, the order of
components is as shown in figure 6.3a and for a d 8 ion, the order is a shown in
Figure6.3b.
Fugures 6.3a and 6.3b Free ion and Crystal Field Terms of
d2 and d8 ions in octahedral Fields.

Free Ion Terms

Crystal Field Ion Terms Free Ion Terms
1 Crystal Field Ion Terms
1 Eg 1
A1g 1 T2g
3
A2g A 1g
3
T1g
1
T2g 1
T2g
1 1
T1g
S 3
T1g 1
S
1
T1g
3
T1g

1
A1g 3T2g 1
1 A1g 3T2g
G 1
G
3
P 1 3
1 1 Eg P
D T2g 1
D
1
Eg

3
F 3
T1g 3
F 3
A2g
2
d ion 8
d ion

Note : The Crystal Field Components of an 3F Term of a 2d-ion occur in the

reverse order in a d8 ion .
Note: In figures 6.3a and 6.3b , we have indicated on the left margins the relative
energies of the free ion terms namely, , 3F,(lowest energy) , 1D , 3P, 1G and
,1S(highest energy).
Note the following points: -
(a) Just as an octahedral field splits d-orbitals into two sets, t 2g set and eg-set, an
octahedral Field splits a D-term into two components , a T 2g component and
a an Eg

Electronic Bands. Electronic Transitions take place between the ground state crystal
field component to various higher energy levels. For example, in a d 2 ion, electronic
transitions take place from the crystal field ground state term 3T1g to higher energy level
components.
Eg
3
T1g(3F) 3
T2g(3F)
3
T1g(3F) 3
T1g(3P)

3
T1g(3F) 1
Eg(1D)

us in , in both d2 and d8 free ions, the Ground state Term is the 3F Term .

SPIN ALLOWED AND SPIN FORBIDEN TRANSITIONS.

A close examination of Figure 6.3a shows that theoretically, we should see a total of 10
transition bands in an electronic spectrum of a 2d ion. In practice we , see only two bands
.
There are two reasons for this:
(i) Selection Rules . There are selection rules which rule out possibility of observing so
many electronic bands .
(a) Spin Allowed and Spin- forbidden Transitions .
According this rule, when an electronic transition takes place between two terms of the
same spin multiplicity, eg from a triplet to a triplet in our case, it is described as being
spin allowed. because it is much more probable to occur the a transition between two
terms of different spin multiplicities. A transition from a triplet state to a singlet implies
coming from a state with two unpaired electrons to a state with paired electrons. As noted
earlier, electron pairing is an energy consuming process and hence, it is less likely to
occur. On the other hand, a transition from a triplet state to a triplet state does not
involve any electron pairing and hence, energetically, it is more likely to occur.
It has a much higher probability of occurring than a transition that takes place between
terms of different spin multiplicity . This is the reason why, in a d 2 ion, only three
transitions have high probability of taking place.
(b) Transition Taking Place Outside Detectable Spectral Range.
In an electronic Spectrum of a d2 ion such as [V(H2O)6]3+, only two peaks are seen in
the visible region even though three spin –allowed bands are predicted. The third peak
lies in UV region where it is obscured by strong charge transfer bands. Hence, reason for
observing only two peaks.
A similar observation is made in electronic spectra of d3 ions such
as V(H2O)6]2+ or Cr(H2O)6]3+.
(c) COMPARISON OF SPECTRA OF d2AND d8 IONS.
From the hole formalism , it follows that a d 8 ion, just like a d2 ion has three spin-
allowed peaks. This happens to be the case and, fortunately, for a shell which is more
than half full , the transitions take place within the visible region. Hence a UV-VIS
spectrum of [Ni(H2O)6]2+ has three absorption peaks at 8,700cm-1, 14,500cm-1 and
25,300cm-1.(Figure 6.4)
Absorbance

Increasing Frequency
Figure 6.4 A UV-VIS Spectrum of [Ni(H2O)6]2+
(c) COMPARISON OF SPECTRA OF d3 AND d7 IONS.
From the hole formalism , both d3 and d7 ions have same number of Terms and hence,
the spectra should have same number of spin allowed peaks. As in the case of a d 2 ion,
the third peak in spectra of d3 ions such [V(H2O)6]2+ or [Cr(H2O)6]3+ occur in the UV
region and are not, therefore, seen in UV-VISBLE spectra of these
ions . Fortunately, the spectra of d7 ions such as [Co(H2O)6]2+ in weak octahedral crystal
fields as is the case for[Co(H2O)6]2+ - show three spin-allowed peaks. For example, this
cobalt(II) ion shows absorption peaks at 8,00cm -1, 19,600cm-1 and 21,600cm-1.
These peaks are attributed to transitions from the ground state to the higher energy
level Terms.(Figure6.5)
 Figure 6.5 Engergy-Level Diagram For a d7 ion in a Weak Octahedral Field.
4
A2g

4
T1g

4
T2g

4
P

4
F 4
T1g
( Note: Only spin allowed Transitions are shown

We stress the importance of weak crystal field because, in a strong field such as the case
2+
in the complex, [Co(NH3)6] , there is only one unpaired electron in the species and
hence, very different type of absorption peaks.
MAGNETIC PROPERTIES OF TRANSITION METAL
IONS.
In chapter five , it was noted that in an ion such as Cr2+, electrons
may occupy the d-orbitals singly or paired depending on the type
of ligand co-ordinated to the metal ion. Thus, in the complex, be
Cr(H2O)6]2+, the electrons occupy the d-orbitals singly since the
water molecules do not produce sufficiently strong fields to force
the electrons to pair up (
 Observed

Expected

Zn(II)
Ca(II)
(Mn(II)
Figure 5.12 a&b) has been reproduced as it occurs in chapter 5.
Figure 5.12 Splitting of d- orbitals by a weak (Figure 5.12a)
and Strong (Fig5.12b) Octahedral Fields for a d4 ion.

eg-set

eg-set

d4 Small 10Dq
d4 Large 10Dq
t2g-set

t2g-set
Figure 5.12a Splitting of d-orbitals Figure 5.12b Splitting of d-orbitals
by a weak Oh-Field.Eg [Cr(H2O)6]2+
by a strong Oh-Field.Eg [Cr(NH3)6]2+
CFSE=(-1.2+0.6)
- o) CFSE= -4Dqx4
=-0.6o. =-16Dq
Generally, a species with unpaired electrons is attracted strongly
by a magnetic field and is described as paramagnetic. Conversely,
a species with all electrons paired up is repelled by a magnetic
field and is said to be diamagnetic.