UNIT-IV: Electronic spectra

In this lecture, you will learn

(i) Salient features of electronic spectra
(ii) Coarse (vibrational) structure of electronic spectra
(iii) Fine (rotational) structure of electronic spectra
(iv) Fortrat parabola
(v) Franck-Condon Principle
1. Introduction:
(i) Electronic spectra arise from transitions between the electronic
states of molecules and are observed in the visible and ultraviolet
regions of E.M. spectrum.
(ii) The electronic transition is accompanied by a number of transitions
involving a vibrational level of the upper and a vibrational level of
the lower electronic state, each of which, in turn, is accompanied
by a number of transitions involving a rotational level of the upper
and a rotational level of the lower vibrational level.
The rotational transitions give rise to a group of fine lines which
constitute a ‘band’. That is a band arises from a particular
vibrational transition, and the bands arising from all the vibrational
transitions constitute a ‘band-system’. Thus, a single-electronic
transition in a molecule give rise to a band-system.

v'=2

v'=1

v'=0

re'

v=2

v=1

v=0

v"=0 progression (v'-progression)

re
(iii) Electronic spectra are studied both in emission and absorption,
and the bands show a fine structure more complicated than in the
vibrational-rotational bands.

(iv) All diatomic molecules exhibit electronic spectra.

(v) The tendency of head-formation is much stronger, and the bands

may be degraded either toward the red or toward the violet.

(vi) Progression: The bands of the system which corresponds to the

same upper vibrational level (v') but different lower vibrational
levels (v") are said to form a v"-progression and similarly, the
bands corresponding to the same lower level but different upper
levels (v') form a v'-progression.

(vii) A group of transitions with the same value of v is referred to as a

sequence.
2. Coarse (Vibrational) structure of electronic spectra:
The total energy E and term value T of the molecule are given by:

E = Ee + Ev + Er

T = Te + G(v) + F(J) -------------------------(1)

Since an electronic transition involves a change in all the three

electronic, vibrational and rotational energies of the molecule, the wave-
numbers arising from an electronic are given by:

 = (Te'-Te") + (G'-G") + (F'-F") ------------(2)

For a given electronic transition, Te'-Te" = e , a constant.

Ignoring the rotational structure of the individual bands (F'-F"=0), the

wave-numbers corresponding to the band-origins of the system are
given by:
 = e + G' (v') - G" (v")

For an electronic transition,

v = unrestricted

A vibrational transition for a given electronic transition is called a

vibroinc transition.
 v'=2

v'=1

v'=0

v=2

v=1

v=0

v = - 1 v = 0 v'=0 progression
sequence sequence

Figure: Some vibronic transitions

 Deslandres Table

In order to analyze these bands, the wave-numbers of the band-origins

are arranged into an array between the values of v' and v", called
Deslandres table, as shown below:

v" 0 1 2 3
v'
0 e + G'(0) - G"(0) e + G'(0) - G"(1) e + G'(0) - G"(2) e + G'(0) - G"(3)
1 e + G'(1) - G"(0) e + G'(1) - G"(1) e + G'(1) - G"(2) e + G'(1) - G"(3)
2 e + G'(2) - G"(0) e + G'(2) - G"(1) e + G'(2) - G"(2) e + G'(2) - G"(3)
3 e + G'(3) - G"(0) e + G'(3) - G"(1) e + G'(3) - G"(2) e + G'(3) - G"(3)
4 e + G'(4) - G"(0) e + G'(4) - G"(1) e + G'(4) - G"(2) e + G'(4) - G"(3)

We see from above table that the constant separation between two
successive ‘rows’ of the table is the separation (in wave-number units)
between the corresponding vibrational levels of the upper electronic
state.

G'1/2 = G'(1) - G'(0) = 'e - 2'ex'e

G'3/2 = G'(2) - G'(1) = 'e - 4'ex'e
G'5/2 = G'(3) - G'(2) = 'e - 6'ex'e
----- ---- ------- ------ ----------

The second difference of successive vibrational quanta is the same and

gives the vibrational constant 'ex'e (anharmonicity constant) for the
upper state.
2G' = 2'ex'e
Similarly, the constant separation between two successive ‘columns’ of
the table is the separation between the corresponding vibrational levels
of the lower electronic state.

G"1/2 = G"(1) - G"(0) = e" - 2e"xe"

G"3/2 = G"(2) - G" (1) = e" - 4e"xe"
G"5/2 = G"(3) - G"(2) = e" - 6e"xe"
----- ---- ------- ------ ----------

And the second difference gives the vibrational constant e"xe"

(anharmonicity constant) for the lower state.
2G" = 2e"xe"

Now from the vibrational levels of each electronic state, the vibrational
constants e' and e" can be calculated.
e' = G'1/2 + 2e'xe'
e" = G"1/2 + 2e"xe"

In the Deslandres table, the bands along the diagonal or along a line
parallel to the diagonal form sequences whereas bands in the horizontal
rows and in the vertical columns form v"- and v'-progressions,
respectively.
3. Fine (Rotational) structure of electronic spectra:
The wave-number of a line of an electronic band is given by:

 = e + (G'-G") + (F'-F")

 = 0 + F' (v', J') -F" (v", J")

Where, 0 is called band-origin. Substituting for F' and F" for the simple
rigid rotator case, the above expression becomes

 = 0 + Bv' J' (J'+1) - Bv" J" (J"+1)

For simple electronic transition 1--1, the selection rule for J is

J = J' - J" = ±1

The transition J = +1 gives one set of lines called R-branch while

J = -1 gives another set of lines called P-branch lines.

R-branch lines:
R = 0 + 2Bv' + (3Bv' - Bv")J" + (Bv' - Bv")J"2 --------(A)
Where J" = 0, 1, 2, 3, 4, ……. Thus R-branch is a series of lines R(0),
R(1), ……corresponding to J" = 0, 1,……

P-branch lines:
P = 0 - (Bv' + Bv")J" + (Bv' - Bv")J"2 --------(B)
Where J" = 1, 2, 3, 4, ……. Thus P-branch is a series of lines P(1), P(2),
……corresponding to J" = 1, 2,……
Since in an electronic transition the rotational constants Bv' and Bv"
belong to different electronic states, they are widely different. As a result
with increasing J", the line-spacing changes rapidly. As we move from
the band-origin, the lines rapidly converge in one branch and rapidly
diverge in the other. In the converging branch, the line spacing after
diminishing to zero, changes sign with increasing J" and so this branch
returns back after forming a sharp head at zero spacing. Thus, in
electronic bands, there is a strong tendency of head formation. On the
contrary, in a vibrational-rotational band, the head formation is not at all
pronounced and usually the head is not observed.

Further, (Bv' - Bv") may be negative or positive in electronic transition;

whereas in case of infrared transition it is necessarily negative. If (Bv' -
Bv") is negative, the quadratic term in equation (A), differs in sign with
the linear term so that line-spacing decreases with increasing J" in the
R-branch. That is, head is formed in the R-branch. Conversely the band
is degraded in the P-branch, i.e. toward the red. If (Bv' - Bv") is positive,
the quadratic term in equation (B), differs in sign with the linear term so
that line-spacing decreases with increasing J" in the P-branch. Thus,
head is formed in the P-branch and the band is degraded toward the
violet.

‘Thus, both red-degraded and violet-degraded bands are observed

in electronic band-systems; whereas only red-degraded bands are
observed in vibrational-rotational spectra”.

In the special case of Bv' = Bv", both the branches will have equi-spaced
lines and the band would be headless.
Both the R- and P-branches can be represented by a single parabolic
equation:
 = 0 + (Bv' + Bv")m + (Bv' - Bv")m2 --------(C)

Where m = J"+1 for R-branch lines

m = -J" for P-branch lines
and m=0 for band-origin

The plot of eq. (C), both when (Bv' - Bv") is negative and when (Bv' - Bv")
is positive, are shown in Fig. 2. These are known as Fortrat parabola.
The vertex of the parabola corresponds to the band-head.

The value of m at which the vertex of the Fortrat parabola lies is

obtained by

d/dm =0

This gives mvertex = - (Bv' + Bv")/2(Bv'-Bv")

Substituting this value of m in eq. (C), the wave-number separation
between band-head and band-origin is given by

head-0 = - (Bv' + Bv")2/4(Bv'-Bv")

head-0 is positive for a band degraded to the red and negative for
the one degraded to the violet. Since for different bands of a band-
system, Bv' and Bv" are different; the distance of the band-head from the
band-origin changes from band to band.

For electronic transition other than 1--1, the selection rule for J is

J = J' - J" = 0, ±1; but J=0 J=0

The transition J = +1 gives R-branch lines

J = -1 gives P-branch lines
J = 0 gives Q-branch lines

Other discussion will follow the discussion for two-branch fine structure
of electronic spectra.
Franck-Condon Principle:

The distribution of intensity among the bands of an electronic-band

system is governed by the Franck-Condon principle.

In 1925, before the development of the Schroedinger equation, Franck

put forward qualitative arguments to explain the various types of intensity
distributions found in vibronic transitions.

According to the Franck, an electronic transition in a molecule

takes place much more rapidly than a vibrational transition so that,
in a vibronic transition, the nuclei have very nearly the same
position and velocity before and after the transition.

This means that in diagrams showing the potential energy curves

of the two electronic states, the transitions must be represented by
‘vertical’ lines.

Fig. 1. Illustration of the Franck principle for (a) r' > r" and (b) r'  r". The
vibronic transition B—A is the most probable in both cases.
In 1928, Condon treated the intensities of vibronic transitions
quantum mechanically. The intensity of a vibronic transition is
proportional to the square of the transition moment Rev, which is given
by

(1)

where  is the electric dipole moment operator and 'ev and "ev are the
vibronic wave functions of the upper and lower states, respectively. The
integration is over electronic and vibrational coordinates.

Assuming that the Born–Oppenheimer approximation holds, we can

write, ev = e v

Then eq. (1) becomes

(2)

First we integrate over electron coordinates e, giving

(3)
Where r is the internuclear distance and Re is the electronic transition
moment given by

(4)

Applying Born-Oppenheimer approximation which assumes that the

nuclei can be regarded as stationary in relation to the much more fast-
moving electrons, we can write eq. (4) as

(5)

The quantity is called the overlap integral. Its square

is known as the Franck-Condon factor to which the intensity of the
vibronic transition is proportional. In carrying out the integration, the
requirement that r remains constant during the transition is necessarily
taken into account.

Thus the relative intensities of the bands in electronic band-system

mainly depend on the Franck-Condon factor and the bands which
have maximum Franck-Condon factor are most probable/intense.

The classical turning point of a vibration, where nuclear velocities are

zero, is replaced in quantum mechanics by a maximum, or minimum, in
v near to this turning point. As is illustrated in following figure, the larger
is v the closer is maximum, or minimum, in v, to the classical turning
point.
 Fig. 2.

Fig. 3: Franck-Condon principle applied to a case in which re' > re" and
the 4—0 transition is the most probable.

Fig. 3 illustrates a particular case where the maximum of the v'=4 wave
function near to the classical turning point is vertically above that of the
v"=0 wave function. The maximum contribution to the vibrational overlap
integral is indicated by the solid line, but appreciable contributions
extend to values of r within the dashed lines.

Clearly overlap integrals for v' close to 4 are also appreciable and give
an intensity distribution in the v"=0 progression like that in Fig. 4 (b).
 Fig. 4 Typical vibrational progression intensity distribution.

If r'e >> r", there may be appreciable intensity involving the continuum of
vibrational above the dissociation limit. This results in a v"=0 progression
like that in Fig. 4(c) where the intensity maximum is at a high value of v;
or it may be in the continuum.

Fig. 4(a) shows the intensity maximum at v'=0 for the case when r'e  r"e.
The intensity usually falls off rapidly in such case for v'>0.

According to the Franck-Condon principle, in general, the most

probable transitions are those in which one of the two turning
points of a vibrational level of one electronic state lies at
approximately the same internuclear distance as one of the two
turning points of a level of the other electronic state, except in case
of v=0 level for which the mid-point rather than the turning point
must be substituted.
 Explanation of Intensity Distribution in Emission Bands: Condon
Parabola
v' = 0 -------- v" (0, 1, 2, …)

v' = 4 -------- v" (0, 1, 2, …)

r'e = re" r'e > r" r'e >> r"