BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 23
04 Mar 2019
AY 2018-19, Sem-II
Spectroscopy of Complexes
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Discussed topics in L-22
• Tetragonal distortions

• Square planar system and energy levels

• Change in square planar energy level

• Octahedral vs. square planar geometry

• Square planar system example

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Comparative d-orbital levels
Regular Distorted Square
Octahedral Octahedral Planar

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Stabilization in distorted octahedron

Calculate CFSE by placing the electrons in these levels

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Square planar energy level
• The dz2 orbital falls the most, as its
electrons are concentrated in lobes
along the z-axis.
• The dxz and dyz orbitals also drop in
energy, but not as much.
• Conversely, the dx2-y2 and the dxy
orbitals increase in energy.

For a d8 system
Octahedral
coordination CFSEsq. pl.
Square
planar
coordination
(xy plane)
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 CFT – Uses and Limitations
Uses
CFT can bring together structures, magnetic, properties and
electronic properties
Trends in CFSEs provide some understanding of thermodynamic
and kinetic aspects of d-block metal complexes
Crystal field theory is surprisingly simple
Limitations
 CFT gives no explanation position of the ligands in the
spectrochemical series – typically due to the description of M-L
interactions as purely electrostatic (no covalency involved)
 Detailed explanation of several observations not possible by CFT
Further modified theories are Molecular Orbital Theory (MOT) and
Ligand Field Theory (LFT): not in syllabus
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Spectroscopy of Transition metal complexes

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Colors everywhere
One of the most characteristic
chemical properties of these elements
is the occurrence of multiple oxidation
states.

Mn(II) Mn(VI) Mn(VII)

Mn(VII)
Cr(VI)
V(V)
[V(H2O)6]2+ [V(H2O)6]3+

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Electronic spectroscopy of complexes
• Studies of electronic spectra of metal complexes provide
information about structure and bonding, although interpretation
of the spectra is not always straightforward.
• Spectra arise because of transition of electrons from one energy
level to another by absorption of EM radiation in the UV-Visible
region
• The spectrum of a colored
solution may be measured
quite easily in a
spectrophotometer using
the Lambert-Beer’s Law
log(I0/I) = A
A = ε.c.l
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Electronic spectroscopy of complexes
• Absorptions arise from transitions between electronic energy
levels:
transitions between metal-centred orbitals possessing d-
character (‘d–d transition bands’)
transitions between metal- and ligand-centred MOs which
transfer charge from metal to ligand or ligand to metal called
charge transfer bands, (CT bands)
• An absorption band is characterized by both the wavelength (lmax)
of the absorbed EM radiation and emax
• An absorption spectrum may be represented as a plot of
absorbance (A) against wavelength (l) or e against wavenumber ,
or A against wavenumber etc.

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Electronic spectroscopy – examples
Absorption of radiation leading to electronic transitions within a
molecule or complex
Absorption Absorption [Ni(H2O)6]2+
104 10
[Ru(bpy)3]2+

~14 000 25 000 50 000

200 400 700
visible UV
UV visible
-ν/ cm-1 (frequency)
λ / nm (wavelength)
UV = higher energy transitions - between ligand orbitals
Visible = lower energy transitions – typically between d-orbitals of
transition metals and between metal and ligand orbitals [Attributes
of MO theory used]
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Electronic spectroscopy - Characteristics
Absorption maxima in a UV-visible spectrum have three important
characteristics
1. Number of peaks (how many peaks?)
This depends on the electron configuration of the metal centre
2. Position of peaks (what wavelength/energy?)
This depends on the ligand field splitting parameter, Δoct or Δtet
and on the degree of inter-electron repulsion
3. Intensity of peaks (How strong/ weak?)
This depends on the "allowedness" of the transitions, which is
described by two selection rules

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Electronic spectroscopy of Oh complex
The energy of the absorption by [Ti(OH2)6]3+, a 3d1 system is
equivalent to the ligand-field splitting, Do

eg eg
hn
Do
t2g t2g

Complex in electronic d-d transition Complex in electronic

ground state (GS) excited state (ES)
For [Ti(OH2)6]3+, lmax = 510 nm
Do is 243 kJ mol-1 or 20 300 cm-1
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Electronic spectroscopy – Observations
Some important points (for which explanations will be given later)
are that the electronic absorption bands (d-d transition) of spectra:
• d1, d4, d6 and d9 complexes consist of one broad absorption;
• d2, d3, d7 and d8 complexes consist of three broad absorptions;
• d5 complexes consist of a series of very weak, relatively sharp
absorptions

Charge transfer bands may appear due to two phenomena: LMCT

or MLCT (details not is syllabus) – highly intense
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Selection Rules in Electronic Spectroscopy
 Laporte ‘orbital’ selection rule: Transitions which involve a
change in the subsidiary quantum number Δl = ±1 are “Laporte
allowed” and therefore have a high absorbance. Thus, allowed
transitions are from s p, p  d, d  f etc. respectively e.g. For
Ca, s2 becoming s1p1, l changes by +1 and ε is very high as it is
Laporte allowed
In contrast d-d transitions are “Laporte forbidden” and ε is less
example of other forbidden transitions from s s, p  p, d  d,
s d, p  f etc.
 Spin selection rule: During transitions between energy levels, an
electron does not change its spin, i.e., ΔS = 0, i.e. Singlet  triplet
are spin forbidden. E.g. Mn2+ high spin complexes are off-white
or pale flesh colored as they have spin forbidden transitions

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Selection Rules: Relaxations
 Spin selection rule: Mixing of singlet and triplet states is possible
sometimes for the 2nd and 3rd row elements but rare for 1st row
elements.
Laporte selection rule: Spin allowed Laporte forbidden
transitions are observed for the d-d bands can be explained by a
mechanism called vibronic coupling involving d-p mixing– e.g. in
centro-symmetric Oh complexes momentary loss of symmetry
due to vibrational motion is longer (t ≈ 10-13 s) than the transition
time-frame (t ≈ 10-18 s) and mixing of d and p orbitals can occur.
Higher extent of d-p mixing is possible for non-centrosymmetric
tetrahedral complexes making them more intensely colored
(Further details on vibronic coupling and d-p mixing are not in
syllabus)

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Ground state terms

Ground terms
for d1-d10
configurations

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 Splitting of terms
In an octahedral field, the ground term(s) will split into different
levels. E.g. for [Ti(H2O)6]3+ which is a d1 system will have 2D as ground
term, will split this into 2T2g and 2Eg levels (Mulliken symbols) in an
octahedral field

Splitting increases in the order

[TiCl6]3-<[Ti(H2O)6]3+<[TiF6]3-
<[Ti(CN)6]3-

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Splitting of terms
Transforming spectroscopic terms into Mulliken symbols

 The S and P terms do not split, rather they will be named

(transformed) accordingly
 The same multiplicity will be used for the split terms also – the
split terms will have the same multiplicity value as that of the
original term
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Splitting of terms – d1
In an tetrahedral field for d1, the ground term 2D will be the same and
will split into TWO levels as 2E and 2T2 with an ordering opposite to
that of the octahedral complex

Ordering of the
2E
g 2E and 2T levels
2T 2
2
will be opposite
to that of
octahedral case,
2D
qualitatively
2T
2E 2g

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Splitting of terms – d1
In an tetrahedral field for d1, the ground term 2D will be the same and
will split into TWO levels as 2E and 2T2 with an ordering opposite to
that of the octahedral complex
We represent the
opposite ordering
2E
g
as a mirror image
2T
2 plot. Hence, D is
not negative on
the other side of
2D D=0
The magnitude of
2E
2T
2g Dt ≠ Do, ONLY
position of levels
are shown here

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HOLE Formulation
When a subshell is more than half full, it is simpler and more
convenient to work out the terms by considering the ‘HOLES’ – that is
the vacancies in the various orbitals – rather than the larger number
of electrons actually present.

In a similar way, by considering ‘HOLES’, the terms which arise for

pairs of atoms with pn and p6-n arrangements, and also dn and d10-n,
give rise to identical terms.

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HOLE Formulation
A d9 system can be considered as the inverted d1 system as far as
energy levels can be considered because d9 system has an electron
vacancy, which is called a ‘hole’.

An inverted energy level relationship exists between dn and d10-n

systems.
A similar energy level relationship exists between dn and d5+n
systems.

d9 = d10-1 = inverted d1 system

d8 = d10-2 = inverted d2 system
d6 = d5+1 = same as d1 system
d4 = d5-1 = inverted d1 system

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Splitting of terms – d9
In an octahedral field for d9, the ground term will be the same 2D and
will split into TWO levels as 2T2g and 2Eg with an ordering opposite to
that of the d1 octahedral complex . 2Eg will be lower and 2T2g higher

2E
2T
2g

2D

2T
2
2E
g

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Splitting of terms – d9
In an tetrahedral field for d9, the ground term will be the same 2D and
will split into TWO levels as 2T2 and 2E with an ordering opposite to
that of the d9 octahedral complex . 2E will be higher and 2T2 lower

2E
2T
2g Thus, for d1 and
d9, inverse
positions are
2D justified for
octahedral and
2T
2 tetrahedral fields
2E
g respectively

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Splitting of terms – d1 & d9
Thus we can represent both these cases in a single diagram – Orgel
Diagram

2E or 2E
g
2T or 2T2
2g

2D

2T or 2T2
2g
2E or 2E
g

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Discussed topics……

Electronic spectroscopy: Aspects

Selection Rules
 Application of term symbols in coordination chemistry
Splitting in Oh and Td complexes
Hole formulation
d1-d9 Orgel diagram

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Announcement
Notice – Assignment Test - 01
ALL Tutorial Sections together
Date: 07 Mar 2019, Thursday
Time: 5.30 pm - 6 pm

Dear Students;
Model question(s) for assignment-01 has been uploaded on
Nalanda. Assignment-1 will be conducted on Thursday (07 March
2019) at 5.30-6.00 pm. Kindly find room details as per your section
number in list uploaded on Nalanda.
Syllabus for assignment-1: Lecture No. 01-22 (as per handout)

With best wishes,

Indresh Kumar (IC, CHEM F111)

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Notice – Assignment Test - 01
Time: 5.30 pm - 6 pm

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