Electronic spectroscopy

Theory of UV-VIS spectroscopy, Term symbols, PES and lasers

 Quantitative analysis: concentration determination.
Qualitative analysis: identification of molecule properties
 General
 The separation between two consecutive electronic states is of the order of 10 -6 cm-1 or more and the transitions between
them lie in the visible or UV regions of the electromagnetic spectrum.

 During an electronic transition, changes in the vibrational as well as rotational energy levels also can take place.
The Born–Oppenheimer approximation
 Electrons and nuclei in a molecule experience same forces of magnitude but nuclei ~ 4 times more

massive, so electrons move much more rapidly.

 Energy of a molecule depends on the relative positions of nuclei. Born-Oppenheimer approximation is that

nuclear and electronic motion are separable and independent.

So the total energy can be expressed as:

 Etotal= Eelec + Evib+ Erot

A change in the total energy of molecule may then be written as;

 ΔEtotal= ΔEelec + ΔEvib+ ΔErot (J)

In terms of wavenumber it is written as;

(cm-1)

The approximate order of their magnitudes are given by;

ΔEelec ≈ ΔEvib x 103 ≈ ΔErot x 106

 So the vibrational level changes will produce a coarse structure and rotational level transitions will
produce a fine structure in the electronic spectrum. So the spectrum is called electronic- vibrational-
rotational spectrum.

 Electronic spectrum can be given by all types of molecules since changes in electronic distribution
involved in electronic level can cause a change in dipole moment.

 This means that homo nuclear molecules (for eg; H2 or N2), which show no rotation or vibration-
rotation spectra, do give an electronic spectrum and show rotational structure in their spectra from
which rotational constants and bond vibration frequencies may be derived.
Vibration Coarse structure

In order to understand the Vibration Coarse structure of a molecule, let us

drop the rotational energy terms from expression of total energy as;

ϵtotal= ϵelec + ϵvib

Where ‘V’ is the vibrational quantum number with values 0,1,2,3 etc, is the
oscillation frequency of the molecule and is its anharmonicity constant.
Let V’’ and V’ be the vibrational levels of the lower and upper electronic states respectively. There are no selection rule
for V’’→ V’ transition.

Every V’’→ V’ transition may take place and large number of spectral lines would be expected following a specific
electronic transition.
Using the equation discussed, the frequency of a spectral line is given by;

…….(1)

A change in vibrational quantum number accompanying an electronic transition does not

follow any selection rules of vibrational spectroscopy. That is all the (v’’→ v’) transitions

are possible. Since most of the molecules are present in the ground vibrational energy

state, the transitions from this level are of considerable energy. The transitions which

originate from v’’= 0 state, labeled according to their (v’,v”) values as (0,0), (1,0), (2,0),

(3,0) are of large intensity. The set of lines corresponding to these transitions are known

as v’ progression as the value of v’ increases by unity for each line in the set. These set

of transitions involving v” = 0 forms a band.

This is because under low resolution, each line of the set appears broad
and diffused and is called v’ progression. The wavenumber of (0,0)
transition can be obtained by substituting the values for v’’ and v’.

(0,0) = …..G(0)……(2)

(0,1) = ….G(1)…..(3)

(1,0) = ]….G(2) …..(4)

It can be seen that the difference between the successive lines is a constant.

-
(0,0) (0,1) =(2) – (3) = ….(4)

-
(1,0) (0,0) =(4) – (2) = ….(5)

This can be tabulated in a table known as Deslandres table. This table is a useful method to assign vibronic
transitions in electronic spectroscopy. In such a table, the frequencies of the lines seen in an electronic spectrum of a
molecule are collected so that the differences in energy between adjacent columns or rows are all the same (within
experimental error). …..Sequence

Note: The lines in a band crowd

more near higher frequencies.
Franck-Condon principle

The Franck-Condon principle states that: an electronic transition takes place sufficiently rapidly that the
nuclei do not change their internuclear positions during the transition. Consequently, when energy is absorbed in an
electronic transition, the nuclei suddenly find themselves in a new force field and at positions which are not in
equilibrium for the new electronic state. This is shown schematically in Fig. 1, in which an electronic absorption from the
ground state appears as a vertical line because of the Franck-Condon principle.
The internuclear separation of the ground state becomes a turning point, the extent of maximum displacement, in a
vibration of the excited state. The vertical transition has the greatest transition probability but transitions to nearby
vibrational levels also occur with lower intensity. Therefore, instead of an electronic absorption occurring at a single,
sharp line, electronic absorption consists of many lines each corresponding to the stimulation of different vibrations in
the upper state. This vibrational structure (or progression) of an electronic transition can be resolved for small molecules
in the gas-phase, but in a liquid or solid collisional broadening of the transitions cause the lines to merge together and
the electronic absorption spectrum is often a broad band with limited structure.
Rotational fine structure of electronic-vibration spectra
Under high resolution of electronic spectra, each line in the spectrum consists of a set of closely spaced lines caused by
the rotational fine structure of electronic-vibration transitions. The total energy according to Born –Oppenheimer
approximation is;
Δϵtotal= Δϵelec + Δϵvib+ Δϵrot (cm-1)

spec = (V’,V”) + Δϵrot

Where (V’,V”) represents total wave number for electronic and vibrational transitions.
Selection rules for rotational transitions depend on the type of electronic transitions.
(i) If both upper and lower electronic states have non-zero angular momentum about the bond axis, the rule is ΔJ =
0,±1, but J=0 to J=0 transition is not allowed. (J=0 ≠ J=0) where J is the rotational quantum number
(ii) If the upper and lower electronic states have no angular momentum about the inter nuclear axis, ΔJ =±1.
 In the second case only ‘P’ and ‘R’ branches appear in the rotational fine structure while in the first case, P, Q and R
branches appear. The wavenumber (V’,V”) is known as the Band origin.

The rotational energy change is given by Δϵ rot = B’J’(J’+1) – B”J’’(J’’+1)

Therefore spec = (V’,V”) + Δϵrot = (V’,V”) + B’J’(J’+1) – B”J’’(J’’+1)……(1)

Where J’’ and B’’ are the rotational level and rotational constant in the lower electronic state and J’ and B’ are the
corresponding values in the upper electronic state. In usual cases B’’>B’
Taking the P,R and Q branches in turn;
1) P Branch: ΔJ = -1, J’’=J’+1…(2)
Applying equation (2) on (1) we will get
Δϵ = P = (V’,V”) – (B’+B’’)(J’+1) + (B’-B”)(J’+1)2cm-1 ……(3) where J’ = 0,1,2,...
2) R Branch: ΔJ = +1, J’=J’’+1…(4)
Applying equation (4) on (1) we will get
Δϵ = R = (V’,V”) + (B’+B’’)(J’’+1) + (B’-B”)(J’’+1)2cm-1 ……(5) where J’ = 0,1,2,...
These two equations can be combined into

P,R = (V’,V”) + (B’+B’’)m + (B’-B”)m2 cm-1 ……..(6) where m = ±1, ±2,...

Positive values of ‘m’ refer to R branch where ΔJ = +1 and negative values of ‘m’ refer to P branch, where ΔJ = -1, ‘m’
cannot be zero.
3) For the Q Branch, ΔJ = 0; J’ = J’’……….(7)
Applying (7) on (1);

Q = (V’,V”) + (B’-B’’)J’’+ (B’-B”) J’’2cm-1 ……(8) where J’’= 1,2,3... (0 to 0 transitions are not allowed).
Coming back to P and R branches, it is observed that P branch appears on the left hand side of the band
centre (second and third terms are –ve) and the spacing increase with increases in the ‘m’ value. The R Branch
appears on the right hand side of the band origin (second term is +ve and also magnitude of the second term is higher
than third term) and the spacing decreases with increasing ‘m’ value so rapidly that after reaching a maximum
value of wave number the spectral lines return to lower wave numbers. The point at which the return occurs ie,
where the spacing becomes zero is called ‘band head’. As the second and third terms of Q Branch lines are –ve they
appear along with P Branch ie on left side of band origin. This is the case when B’’>B’ (The internuclear distance is
higher in ground state than in the excited state)
 1 2 3 45 67 m
R Branch

m
-8 -6 -5 -4 -3 -2 -1
-7
P Branch

J"
12 11 10 9 8 7 6 54 3 1
Q Branch

(V',V")
Band Head

(B’’>B’ -The internuclear distance is higher in ground state than in the excited state)
In this case where B’ < B’’ the band head appears in the R branch on the higher wave number (right)side of band
centre, such a band is said to be banded towards the violet (band head) and the tail of the band points
towards the low frequency side (red).
If electrons excited are from antibonding molecular orbitals, bonding becomes stronger and
internuclear distance decrease in the excited state. So B’>B’’ and hence the spacing increases with the
increasing ‘m’ values in the ‘R’ branch. In the P branch, spacing decrease with increase in ‘m’ value reaches
the band head and returns to higher frequency side or the rotational fine structure is shaded to the right or
violet.

B’’>B’ B’>B’’

R on right..spacing P on left..spacing
decreases decreases
P & Q on left R & Q on right.
Band head at right R Band head at left P
 Fortrat Parabolas

Wavenumbers of lines in P, R and Q branches can be expressed with continuous variables p and q as

P,R = (V’,V”) + (B’+B’’)p + (B’-B”)p2…………………………………(1)

Q = (V’,V”) + (B’-B’’)q+ (B’-B”) q2………..………………………….(2)

Where p takes both positive and negative values whereas q takes only positive values. Equations (1) and (2) are
equations of parabolas .These parabolas are known as the Fortrat parabolas. The PR parabola intersects the axis at N,
the band origin. Its vertex H is the band head of the band. Since we have a turning point at the vertex, we have

Thus, the position of the band head corresponds to

Phead = ˗ ………………………………………………………….(3)
Using equation (3) in (1), we have

(V’,V”) =

For B’˂ B” ,the right side is positive. Thus the head of a band is at a higher wave number than the band origin.
This shows that the band head appears in the R branch with positive p values. When B’˃ B”, the band head occurs
in the P branch with negative p values.
Dissociation

At absolute zero, the energy of a molecule is the one contributed by the vibrational zero point energy ϵ o (cm-1). The
amount of energy required to break a stable molecule AB in the V = 0 vibrational state into two atoms A and B, each in
the G.S, is known as the dissociation energy D0. The figure given shows dissociation energies D o” and Do’ of the G.S and

E.S of molecules, respectively. The equilibrium dissociation energy De is related to Do (for both lower and upper
electronic states) as

De = Do + ϵo (cm-1)…….(1)
Photo-dissociation

Normal electronic spectra of a diatomic molecule consists of a series of vibrational transitions with or without rotational
fine structure and then a continuum. The lower end of the continuum gives the energy required to produce dissociation with
zero kinetic energy for the dissociation products (atoms).

Generally a molecule in the state corresponding to the continuum limit dissociates into a normal atom and an excited
atom with excitation energy Eex.

This Eex is the total energy of the dissociation products in the upper state (photo-dissociation by excitation) minus the total
energy of the dissociation products in the lower state. When the molecule dissociates from one of the continuum states, the
energy in excess of continuum limits appears as kinetic energy. Thus;

…….(2) where is the dissociation energy in the G.S.

Further
………..(3) where is the dissociation energy in the upper state.

Therefore
…..(4)
Value of known from electronic spectroscopy whereas the value of is known from atomic spectroscopy. After using
these values, one can calculate the dissociation energy.

The vibrational energy ϵv of a diatomic molecule is

ϵv = (V+1/2) - …..(5)

The separation Δϵ between two successive vibrational states is given by;

Δϵ = ϵv+1- ϵv = …(6)
The separation decreases linearly with the increase of value of corresponding to the dissociation limit (Δϵ=0) we
have;

….(7)

…….(8)

The vibrational energy for is the dissociation energy De. Thus substituting (8) in (5) we have

De = ……..(9)

De = cm-1……..(10)

From the known values of , the value of De can be obtained and finally the value of
Predissociation

A continuum on the high wavenumber side in

electronic spectra corresponds to ordinary
dissociation. However in certain cases the
rotational fine structure is diffused or a continuum
is observed for intermediate changes as shown in
the fig. Occurrence of such diffuse structure or a
complete continuum below the true dissociation
limit is known as predissociation.
A simple case of predissociation may be understood with respect to the Morse curves X,A and B as shown above. Here the
excited state B is not stable as it has no minimum. Let us consider a transition from the curve X to A. In some cases it is
possible to cross over to the curve B and this leads to the molecule to dissociate. When this radiationless transition occurs
from the curve A to B, there is no rotation of the molecule as the time required for a molecular rotation is 10 -10s. However the
vibrational energy whose structure is quantized, gives a diffused band structure as the time required for a molecular
vibration is 10-14s. At transitions to higher vibrational energy levels (above the one in which cross over occurred) will give
normal vibrational electronic spectrum with rotational fine structure as the molecule spends more time as the extreme ends of
the vibrational motion and minimum time near the crossing points.
Birge and Sponer method

As the vibrational quantum number increases, Δϵ (ϵv+1- ϵv), the energy difference between the successive levels decreases.
At high ‘v’ values, the vibrational bands overlap and merge together and will become a continuum. If Δϵ is plotted against
the vibrational quantum number V, we get a curve as shown below. Birge and Sponer observed that area under the Δϵ
versus V graph gives the disassociation energy directly. This is the Birge and Sponer method.