UNIT-III: ELECTRONIC SPECTROSCOPY& MAGNETIC PROPERTIES 2.

SELECTION RULE
Basic:1.Physical Laws Should not be violated in the Universe: That is universe is made of i. Spin Selection Rule The overall spin S of a compound must not change during an
physical laws (Newton-classical, Einstein, Thermodynamic, quantum) 1.Structure: electronic transition, hence, ΔS = 0; singlet → singlet; triplet → triplet-allowed
Individual/Family-Atom/Molecule;2.Theories: Newton(Classical-Old) / Einstein/ Quantum
(Resonance-Matching) /Big Bang/ String/ My theory-Entanglement-Causality.3.Newton- Two
body-Apple(System) / Earth(Surrounding/ Environment-Uniform) To animals/ birds(living) -
Darwin Theory, To society-Marx; 4. Individual/Atom: :Name/State-Elements-H; States 1.
+ - .
Atom-H2. Ions-H ,H ,3.Radical-H 5.Family-Molecule-:Name-Based on Relationship (Bonds)-
Molecule-H2-Covalent molecules (organic),ionic & coordinate (Inorganic) 6.Strength of
Relationship: Strong-Stable/week-unstable-mobility of electrons7. Theories: Explains the ii Angular Momentum Selection Rule: The change in total orbital angular momentum can
relationship in atom/molecule 7. Need/Problem: Unable to explain spectra/Explain(UV-VIS) be ΔL=0, ±1, but L=0 ↔ L=0 transition is not allowed
8. Use/Application: To find the geometry
1. INTRODUCTION TO UV-VIS SPECTROSCOPY
ELECTRONIC SPECTRA (OR) ULTRAVIOLET-VISIBLE SPECTROSCOPY (OR)
ULTRAVIOLET-VISIBLE
i.Spectrophotometry (UV-Vis or UV/VIS): This is the spectrum of molecules in UV-Visible
region. This is due to the electronic transitions in the molecules. The spectrum is observed in
the region of 200-800 nm. In this, the visible region is 400-800 nm and UV region is
200-400 nm. The energy of the spectral line is; ΔE=hυ.
200-400 nm-Deuterium lamp; 400-800nm – Tungsten lamp
ii.Selection Rule:1. The change in angular momentum is 0, ±1
2. The spin of the two states must be same Δs = 0.
3. Transition between same symmetry is prohibited. g→g; u→u- not allowed; g→u - allowed
iii.Types of Electronic Excitation
The electronic transitions are four types. They are, σ* l=1 l=2
2 2 2
σ→σ*; π→ π*,n → π* , n → σ* π* px py pz dxy dxz dyz dx -y dz
a. σ→σ*Transition: This is the transition of electron +1 0 -1 +2 +1 0 -1 -2
from bonding sigma orbital to anti bonding sigma n iii. Laporte/Symmetry Selection Rule:
orbital. It requires higher energy and appears in the
UV region.(below 200 nm) eg. Methane π
λmax = 122 nm σ
b. π→ π* Transition: This is the transition of electron from bonding pi orbital to anti bonding
pi orbital. This type of transition is present in unsaturated compound.
Eg. 1,3-butadiene λmax = 217 nm
c. n → σ*Transition: This is the transition of electron from non-bonding orbital to
anti bonding sigma orbital. This type of transition is present in saturate halides, alcohols.
Eg. Methanol λmax = 174 nm
d. n → π* Transition: This is the transition of electron from non-bonding orbital to
anti bonding pi orbital. This type of transition is present in aldehyes and ketones.
Eg. Acetone λmax = 270 nm
The order of energy is; σ → σ*> n → σ* > π → π* > n → π*

Spectra –UV-VIS-IR UV-VIS VIS Octahedral

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 3. RUSSELL-SAUNDERS (OR) L-S, J-J COUPLING, MICROSTATES, TERM SYMBOLS, 17.J-J Coupling: It is the total orbital angular momentum and total spin angular
SPLITTING OF TERMS, HOLE FORMALISM momentum. In this each electron is assigned an angular momentum J composed of its
1. The four quantum numbers n, ℓ, m, and s specify quantum state of a single electron in orbital angular momentum l and its spin s.
an atom called wave function or orbital. 18. Term symbol is the electronic state due to spin and orbital angular momentum.
2.Quantum mechanics explains quantization, superposition, entanglement and
uncertainty better than classical mechanics (Newtonian Mechanics).
4. Quantum numbers could not explain the spectral lines.
3.Quantum coupling is interaction between the quantum states explains system (Electronic
States)behavior..
4. There are TWO types of coupling to explain the spectral lines.
5. The first is L-S coupling or Russell-Saunders coupling which explains the spectral lines
st
of light atoms (At.No.30-1 row transition metals).
5.Another coupling is called J-J coupling which also spectral lines of heavier atoms.
6.The coupling is between angular momentum of orbital and spin motions in
many-electron-atoms combine to characterise the electronic states of atoms.
7.The interactions of three types i.spin-spin coupling ii.orbit-orbit coupling iii.spin-orbit
coupling
8.The energy order is; spin-spin coupling > orbit-orbit coupling > spin-orbit coupling.
9. For first row transition metals L-S coupling is sufficient to explain the spectral lines.
10. For heavier atoms where spin-orbit (J) is used.
11. Spin-Spin coupling (S =2s+1) The total spin(S) is the resultant spin quantum number for
a system of electrons. S arises from adding the individual ms of electrons.
12.Orbit-Orbit coupling (L): The total orbital angular Total Orbital Momentum
momentum quantum number (L) defines the energy state for a
system of electrons. These states or term letters are L 0 1 2 3 4 5
represented as S P D F G H
13.Spin-Orbit coupling (L-S): Coupling occurs between the resultant spin and orbital
momenta of an electron which gives rise to J the total angular momentum quantum number.
Multiplicity occurs when several levels are close together and is given by the formula (2S+1).
(2S+1)
14. The Russell Saunders term symbol is: L
1 2
15. Example, for a d configuration: S= + ½, (2S+1) = 2; L=2 and the Ground Term is D
16. The Russell Saunders term symbols for the other free ion configurations are

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 19. Microstates are the different ways in which the electrons can occupy the orbitals  5.The x-axis axis is the size of the ligand field splitting energy Δo
specified in the configuration  6.The y-axis axis is energy.
 7.The diagram is qualitative, and show only the states of highest spin multiplicity 2S+1.
 8.They combine octahedral (Oh) and tetrahedral (Td) cases together for the same ground
state free-ion term.
9. The gerade/ungerade labels are omitted
 1 6
10 The D- Orgel diagram, tetrahedral d /d and
9 4
octahedral d /d on the left side, and
4 9 6 1
tetrahedral d /d and octahedral d /d on the
right side.
 11.For the F/P Orgel diagram,
2 7 8 3
tetrahedral d /d and octahedral d /d on the
3 8
left side, and tetrahedral d /d and
7 2
octahedral d /d on the right side.
20. Holes are unoccupied electron sites 12. The hole formalism is
.5. TANABE SUGANO DIAGRAM
 1. Tanabe Sugano diagrams show both spin-allowed and spin-forbidden transitions.
 2. They also show both high-spin and low-spin situations, and are separated out into different
diagrams for each dn case.
3. It is more informative, and quantitative.
4.It is more flexible than Orgel diagrams.
5. Example for d4 octahedral complexes:
6. General features of the diagram are
5 3
7. The ground term ( Eg for high-spin, T1g for low spin)
 8.The x-axis is Δo/B and y-axis is
unitless energy scale E/B relative to the ground state,
−1
where B is a "Racah parameter" in units of cm .
 9. The vertical line divide the weak-field and strong-field limits.
 10. To its left are the weak-field (high-spin) terms, and right is strong-field (low-spin).
 11.Solid curves are labeled by excited-state term symbols correlating with spin-
allowed transitions.
4. ORGEL DIAGRAM
1. Orgel diagram is used to explain the UV-VIS spectra of coordination compounds.
 12. Dashed curves for spin-forbidden transitions.
n
2. Orgel diagram explains the spin-allowed transitions and high spin complexes. 13. Unlike Orgel diagrams, these are separated by d configurations, rather than which ground
n state free-ion term.
3. It gives general structure for many d system in one diagram.
14.There are diagrams for d2→d8 octahedral complexes, or d8→d2 tetrahedral complexes.
3.These are separated into one D diagram and one F/P diagram.
6. 10 Dq and β
4. It is less informative, and more qualitative.
1. Crystal Field Splitting Energy (10Dq): In CFT the ligands are considered as point
charges. The interaction between the ligand electrons and the metal electrons split the metal
d-orbitals into t2g and eg. The energy difference between t2g and eg is 10 Dq.
2. Racah Parameters: Racah parameter explains the effect of electron-electron repulsion
within the metal complexes. The Racah parameters are A, B and C. Tanabe-Sugano
diagrams energy is related to B value. A is same for all metal centre and C is 1/4B.
B represents the bond strength between the ligand and metal. Comparisons between the B
D F,P Oh, Td values of free ion and complex is called the nephelauxetic ratio, the effect of reducing
General features of the diagram are: electron-electron repulsion via ligands. β=βcomple/βfreeion

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7. Effect of John-Teller distortion 11.MAGNETIC PROPERTIES
Distortion: Copper (II) is squar plane in 1.Diamagnetic-paired electrons; 2.Paramagnetic-One unpaired electron
nature due to John-Teller distortion. 3. Ferromagnetic-More than one unpaired electron

8.CHARGE-TRANSFER
SPECTRA(KMnO4-Intence Colour):

12.CRYSTAL FIELD THEORY – SPLITTING IN DIFFERENT FIELDS

9.ELECTRONIC SPECTRA OF LANTHANIDE COMPLEXES

10. NEPHELAUXETIC EFFECT