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The Franck-Condon Principle in Diatomic Bound-Free

Transitions

Conference Paper · June 1977

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 Colloques Internationaux du C. N. R. S.
N° 273 - ETATS ATOMIQUES ET MOL~CULAIRES COUPL~S A UN CONTINUUM
ATOMES ET MOL~CULES HAUTEMENT EXCIT~S

The .Franck-Condon Principle in Diatomic Bound-Free Transitions

Joel B. Tellinghuisen
Department of Chemistry
Vanderbilt University
Nashville, Tennessee 37235

ABSTRACT

Intensity factors for molecular transitions are determined by symmetry-

based selection rules and Franck-Condon terms, the latter being certain

squared radial overlap integrals. The Franck-Condon principle has long

been a valuable qualitative aid in the interpretation of band spectra associated

with bound- bound radiative transitions in diatomic s, When the transition in

question is b oun d-Tr e e or free-free, the spectrum is diffuse; and the Franck-

Condon principle becomes practically the only effecti:""e tool for quantitative

analysis. Loosely speaking, diffuse spectra may exhibit two kinds of structure

-- "reflection" structure and "interference" structure. In the former case the

spectrum is roughly the reflection of the initial level's radial probability

distribution onto the final state's potential curve. Interference structure is

a more subtle consequence of phase relations between initial and final radial

wavefunctions. The conditions for occurrence of these types of structure will

be discussed with reference to observed transitions in the halogens, the rare

gas halides, and the alkali d irn e r s , Interference structure is also prominent

in the Franck-Condon terms for nonradiative bound-free transitions or pre-

dissociations. As examples predissociations in 12 and N2 + will be discussed.

 INTRODUCTION

The Franck-Condon principle is such a valuable and well-known spectro-

scopic concept that its use in interpreting spectroscopic intensities is now

automatic. The essence of Franck's idea was that the relatively massive

nuclei do not alter their positions or momenta while the light, facile electrons

change orbitals in an electronic transition. Of course the same notion is the

underpinning of the Born-Oppenheimer approximation. which serves as the

starting point in quantum mechanical treatments of molecules. Thus it was

natural that Franck's idea would soon be given a firm wave-mechanical basis.

That step was taken by Condon in 1928, only three years after Franck stated

his principle. For half a century the Franck-Condon principle has provided

guidance in the interpretation of conventional band spectra. Today spectros-

copists use the detailed results of a band spectrum analysis to calculate

numerical Franck-Condon factors which can then be reliably employed in

quantitative intensity work. For diatomic molecules the prodecures for such

calculations are now well developed and documented and will not be discussed

further here.

The foregoing comments pertain to discrete or bound-bound spectra.

Many electronic states are vibrationally unbound or only weakly bound. When

such states are involved in radiative transitions, the result is a diffuse spectrum,

which may display complex structure but certainly not the wealth of lines

characteristic of discrete spectra. In such cases all of the information about

the unknown potential curves is contained in the intensity distribution as a

function of wavelength or frequency. In other words the Franck-Condon prin-

ciple may be the only effective tool for analyzing such a spectrum. Similarly

in the case of predissociation, where a bound state decays through interaction

with the vibrational continuum of a second state, the latter's potential curve
 319

may be deducible only through the Franck-Condon dependence of the pre-

dissociative decay rate.

This kind of application of the Franck- Condon pr inciple to the quantitative

analysis of diffuse spectra and predissociations in diatomics has only recently

begun to be exploited by spectroscopists. I intend to illustrate these methods

by discussing several cases I have found interesting. My approach will be

more pictorial than mathematical. All of my examples involve a single type

of matrix element, of form < ef lWei vi> , in which Vi and E.

f
refer to the

radial wavefunctions for the molecule in some initial bound v;'brational level

and some final unbound level, respectively. The operator We may take one

of several forms -- e. g. the dipole strength as a function of internuclear

distance R for radiative coupling with the continuum, or the derivative operator

a/oR in certain p r e d i s s oc ia t ion s , In many of these cases one can use the

R-centroid approximation to express the integral as a product of an "average"

operator and a Franck-Condon overlap, W (R) x < E I v. > , where R =

e f 1

<£OfI R I Vi> / <£Of I vi>. In the cases I will discuss,the transition rates can

be well approximated by the Golden Rule, which means the actual quantity of

interest is the absolute square,

(1)

Here the second factor on the right is the Franck-Condon density (FCD),

analogous to the Franck-Condon factor (FCF) which occurs in the treatment

of perturbations or radiative transitions between two bound states. All of

the results I will discuss are the outcomes of "computational experiments"

performed using numerical methods on a computer. Mathematical details

can be found in the references and the works cited therein. The examples I

will use are those most familiar to me through my own work and are not

meant as an exhaustive survey of such work.

320

RADIA TIVE TRANSITIONS

Figure 1 serves to illustrate a particularly simple kind of structure that

may occur in bound-free radiative transitions -- reflection structure. The

visible-infrared absorption spectrum of 12 is comprised of three overlapping

transitions, two of which are almost entirely bound-free (A f- X and Inu~ X)

and one which is mainly discrete, but with an adj oining continuum. 1 All three

of these transitions involve absorption to an upper state which slopes steeply

in the Franck-Condon region, and all show a simple bell-shaped spectrum in

low resolution. Such spectra are called reflection spectra,because they can

be obtained to a good approximation by simply reflecting the probability den-

sity for the v!' wavefunctions onto the upper potential curve. 2 This point is

more evident in the v"-resolved spectrum of Fig. 2. Note the occurrence of

a single peak for v" = 0, two for v" = 1, and three for v" = 2. In this case

Fig. 1. Visible-infrared absorption spectrum of 12, showing contri-

butions of three overlapping transitions. Relevant potential curves
are shown to the right.
 321

Fig. 2. Con-
tributions to
1rrut- X spec-
trum of Fig. 1
from v!' = 0, 1,
and 2.

e:

4500 5500
~(A)

the Boltzmann-weighted contributions from the different v" levels add to give

a single, slightly asymmetric peak in the spectrum. The shape of this peak

is related to the slope of the upper curve: The steeper the curve, the broader

the peak. The area under the peak is determined by the electronic character

of the transition. (The latter point is a consequence of the important closure-

based sum rule, which states that ~ I<vf I vi>12 + f 1<E.f I vi>12 dEf = 1.)

Reflection structure is displayed in the bound-bound portion of the

B.-X spectrum also. Figure 3 shows the FCD for v" = 0, 1, and 2 in the

vicinity of the band convergence limit. 3 (For the discrete region the FCD

is obtained by dividing the FCF by the energy separation between Vi levels. )

Note that the FCD extrapolates smoothly from the continuum into the discrete

spectrum, showing again that in this type of transition the gross spectrum

is determined mainly by the shape of the upper potential curve in the FC

region, irrespective of whether the upper state is bound or unbound.

322

The bound-free emission spectra of

the rare gas halide excimers display a

E
~u
more complex structure, as illustrated 2

4
for XeBr in Fig. 4. The vi-decomposed 'ii

o
~
spectrum in Fig. 5 reveals that this struc- ...
Ii
Ii
ture is again of the reflection type. How- ..
o
u
fi
.::
ever here the potential curve for the final

state is relatively "flat" in the FC region,

so that the structure inherent in the indi- Fig. 3. FCD for 12 B~X
absorption near photodissociation
vidual Vi spectra persists with Boltzmann limit.

averaging, giving subsidiary shoulders and

Fig. 4. B-4X emission

spectrum of XeBr at
...
>
iii
high pressures .
...o
z
Fig. 5. (below) Decom-
calc, position of spectrum in
Fig. 4.
2750 2800 2850

peaks to the blue of the main peak. The more

complex structure present in a spectrum of

this sort can permit a more detailed deter-

mination of unknown potential curves than

is possible for the simpler absorption bands >-

!::
V>
z
of the type illustrated for 12 in Fig. 1. We w
Cl

have analyzed the strong bands (B --JX) in the

high-pressure emission from XeBr, Xel, and

2750 2850
KrF and are examining these and other systems

in other molecules of this group. Recently

 323

several laboratories

h~ve reported very

v' = 10
similar emission spec-
5-7
tra for CsXe.

What happens to

the individual Vi spectra

5

as we go to progress-

ively higher Vi levels

in a system of this sort? III

C

---
<II 2
I will try to answer this C

question with some cal-

culations done for KrF,

which has become the

source of an important
o
new UV laser. The KrF

spectrum is similar to

that of XeBr, except 2300

that the sub sidiary peaks

are bett er resolved because Fig. 6. B .....X emission spe ct r'a calcu-
lated for several Vi levels in KrF.
of the lower reduced mass and

higher vibrational frequency in KrF. Figure 6 shows spectra calculated for

Vi = 0, 2, 5, and 10. Note that (a) the spectra have a roughly constant long-

wavelength limit and spread out to the blue as Vi increases, and (b) the re-

flection structure which is quite evident for Vi o and 2 has begun to go over

into what I call interference structure for Vi = 5 and 10. Both results are due

to the occurrence of a maximum in the difference potential, V(R) = UX(R) +

E(v') - UB(R). I will return to this point momentarily, but first let me call
324

your attention to the weak "extra" peak present in the spectrum for Vi = 2.

On close inspection this interference peak is seen to be present ,even for Vi = O.

In fa ct for appropriate potential curves one can obtain quite pronounced structure

for Vi = O. I illustrate this point with Fig. 7, in which the upper state is rep- --
resented by a harmonic potential, and the lower is taken to be a constant,

U( R ) = 0, with an infinite wall at small R. The Vi = 0 wave£unction is thus a

simple Gaussian, and the lower-state wavefunc tl ons are sine waves, "'~'(R)

= a sin k~ (R-Rco) , where the wave number k~ is proportional to ~l/2 and

-1/4
the amplitude goes as ~ . As e increases from zero, a peak occurs in

the spectrum when the first peak in "/~'(R) coincides with the peak in "'~(R).

As £ increases further, ""~(R) contracts on the R-axis and decreases in

Fig. 7. Model
potential diagram
illustrating or-
igin of inter-
ference structure
o
in emission from
Vi = O.
E
(em'>

20 \

,\
\\ I

'"
\I
\
0

3
R(A>
 325

amplitude. As it does so, its peaks come successively in and out of phase

with the peak in '¥~(R), giving very sharp structure in the spectrum.

Incidentally I should mention that Condon recognized the possibility for

occurrence of such structure and referred to this phenomenon as "internal

diffraction." In fact the reflection principle may be viewed as a limiting

case in which the spectrum is dominated entirely by the central diffraction

maximum.

Spectra such as those implied by Fig. 7 have not yet been observed

and identified for such small Vi quantum numbers, but their analogues

for high Vi have been studied in several cases. One good example is the

E ....B fluorescence spectrum in 12, obtained by sequential two-photon exci-

tation of Vi - 52 in the Estate. 8 The emission process is illustrated in the

potential diagram of Fig. 8. Interpreted classically, the Franck-Condon

principle dictates that the emission terminate on the dashed curve VCR) (the

previously mentioned difference potential), E.

4&

which is the locus of points that conserve

H
nuclear position and momentum in the t r arr-

sition. Thus we see that the spectrum is

42

discrete at short wavelengths, correspond- t /,- ,

ing to transitions which terminate in the "O\"'f
22 .. l<_ __.~~J
...
.. Ee
/!I,
I I.
I'
\
•\
i..
~
bound region of the B- state well, and diffuse I R, R2 \ !
20 : \
:··-VIRI
at long wavelengths where the transitions
I
I
I
end in the vibrational continuum of the B IS

state. Of course the quantum mechanical

1&

overlap integrals are taken ov~r all positive

RIAl

R. However, for a given B-state energy EB Fig. 8. 12 potential diagram

326

the main contribution occurs near R*, .the root of V(R) = EB, where the E-

and B-state wavefunctions have the same periodicity. If additionally the two

wavefunctions are in phase at R". a spectral peak occurs at frequency I) =

EE - EB• For unbound levels below the extremum Vmax(R), two regions of

R contribute significantly to the overlap. These contributions may add con-

structively or destructively, and the result is the characteristic modulated

9
interference pattern evident in the E 4B diffuse spectrum (Fig. 9). In semi-

classical jargon, Rl * and R2* in Fig. 8 are called points of stationary phase.

This type of spectrum has been observed in other transitions which

display maxima in their difference potentials, for example the UV McLennan

bands (D -+X) of 12, first reported over 60 years ago, first correctly explained

by Mulliken in 1971,10 and treated in more detail by myself recently. 11 Structure

of a similar origin occurs in the low-pressure spectra of the rare gas halides. 12

In this case what one sees is the persistence of the modulation envelope, as

the fine oscillatory structure is washed out by extensive averaging over the

(Vi, JI) levels. 13, 14 As a first approximation I find that a roughly uniform dis-

tribution of the energetically allowed Vi levels must be taken to satisfactorily

replicate the limiting low-pressure spectra. 14

>
-
I-
If)
Z
W
I-
Z

Fig. 9. 12 E --> B bound-free fluorescence spectra.

 327

What happens
I·

when the difference ,

I
Fig. 10. CS2 spectra 7
potential is mono-
, produced by optical ex-
citation at the indicated
, r\' wavelengths (A) .
tonic? For low
• 1 \'
initial v levels one '/ 1.

again observe s re-

:1 \
flection structure.
~
As Vi increases,
(
the interference
I
character wins out

eventually, but the

spectrum displays

only the oscillatory

structure, not the

modulation enve-
17000
lope. Spectra of

this type have been observed in a number of cases, including transitions in

I 2' 11 Mg2'·'15 C s2'7,16 an d th e rare gas h ales.'

lid 12 14 Th e C S2 spectra

obtained by Exton and Snow7 using argon ion laser excitation at several wave-

lengths are shown in Fig. 10. Note the nearly constant long wavelength limit

to these spectra and particularly the decrease in the spacing of the spectral

peaks with increasing excitation energy. The latter property is a sure in-

dicator of interference rather than reflection character in the spectrum.

If the difference potential shows more than one extremum, or three

or more points of stationary phase, the spectrum for the relevant range of

continuum energies can become quite complex. I know of no case of this

type which has been identified experimentally, but I have done computations
328

covering this situation. The results are not so easily explained in qualitative

terms so will not be presented here.

PRED1SS0CIATI0NS

1 turn now briefly to two interesting cases of bound-free transitions of

the predissociative type. In predissociations we have the additional condition

that energy must be conserved within the molecular system, and any Franck-

Condon structure is inherently of the interference type. My first example

concerns the now familiar Band Inu states of 12, Evidence for the occur-

rence of a weak predissociation in the B state of 12 f ir sr b eg an to emerge

about ten years ago, when lifetime studies showed a puzzling vi-dependence

in the B- state unimolecular decay rate. Quantum yield measurements cor-

roborated the lifetime results, and the predissociation was attributed to the

'n., state. 17 I subsequently investigated the FC dependence of this process

using the potential curve obtained for Inu in the analysis of the absorption

l
spectrum. The correct mechanism of the B ->lnu predissociation has only

recently beert elucidated in very nice work by Broyer, Vigue, and Lehmann, 19

who have been able to attribute the process to hyperfine coupling between the

two states. However the FC dependence remains roughly as I determined it

in Ref. 18.

In Ref. 1 the In curve was represented as a simple repulsion curve

u

of form cn/Rn, and values of nand c were deduced by matching computed

n

spectra to experiment. The preferred value of n was n = 9. Figure 11 shows

this curve and the corresponding best curves for n = 8 and 10, where they

cross the inner branch of the B curve at low v , Figure 12 illustrates the

vibrational dependence of the FCD for predissociation to the V8 and V 10

curves as well as to a V 12 repulsion curve which lies entirely to the left of

 329

Fig. 11. B and In

u
potential curves of
12 in vicinity of cros s-
ing point.

the B curve and a V6

curve which cuts the

attractive branch of B iE
(.)

near v = 5. Note the v'

strong oscillatory de-
10
pendence for the last

of these, as the bound 5

and free wavefunctions
o
move rapidly in and
2.80 2.90 3.00
out of phase with in-
r t A)
creasing v. This phase
v'
dependence is much

less pronounced for the

8
inner branch crossings,

and for the V12 curve

6
a single peak appears

in the FeD plot. Note

Fe
also that in every case

the FeD dwindles near

the B-state dissociation

Fig. 12. FeD for

B- state predis soc i at i on 4000 5000 6000 7000
to several different
unbound curves. Ec
330

limit. This occurs because the bulk of the probability density resides near

the outer turning point for these very high v levels, and overlap between these

large-R peaks in -¥B(v) and the rapid).y oscillating free wavefunct l on is very

weak.

My final example is the predissociation of the C state of N2 +. Evidence

for this process came from C->X emission studies by Govers and colleagues. 20

One surprising result of these studies was a strong isotopic dependence for

21
the three species 28N2 +, 29N2 +, and 30N2 + Lorquet and Lorquet were

able to account for the observations with a mechanism of. accidental predis-

22
sociation, but Albritton and I found this process to be highly happenstancical

and suggested an alternative mechanism -- homogeneous predissociation to

the B-state continuum. Although the final word on this process is still not in,

I think it likely that C -> B account s for at least a maj or portion of the C-

state predissociative decay.

10.--.---'---'---r--'---~~

70

50

30

v
I
I
I
10 I
v
v

R(A)

Fig. 13. Potential curves for B Fig. 14. Franck-Condon term

and C states of N2 +. for C ....B p r e d is s oc iat l on of
N2 + vs internuclear distance
for B state.
 331

Figure 13 illustrates the Band C curves of N2 +, as obtained from

RKR calculations, and a Morse approximation (dashed curve) to the B

state employed in some of the model calculations. Since the Band C curves

lie some distance apart, C-+B predissociation would appear at first glance

to be exceedingly weak on Franck-Condon grounds. However a combination

of factors makes this process potentially significant. The operator We is

in this case the product of an electronic term and (3 loR, so the Franck-

Condon term is slightly different from the FCD encountered in previous

examples. Let us perform the following computational experiment: Fix

the C curve and observe the variation in the FC term as the B curve is

translated along the R-axis. Decreasing from large R, where the repulsive

wall of B overlaps the inner branch of C, we find the FC term first drops

monotonically by some 15 orders of magnitude, then begins to rise again

in oscillatory fashion. Here again phase relations between the bound and

free wavefunctions come into play. Moreover when we examine the isotope

dependence we find it appreciable, as shown in Fig. 14. By means of slight

adjustment of the repulsive wall of the B curve, we were able to obtain

qualitative agreement with experiment. In subsequent work I explicitly in-

eluded the electronic part of the operator We' as determined by Roche and

23
Lefebvre-Brion, and was able to get quantitative agreement. In this case

the structure in We(R) greatly enhances the overlap between the nearly or-

24
thogonal wavefunctions of the two states. Recent lifetime studies by Erman

place the decay rate somewhat higher than previous estimates, but still

generally consistent with the C ....B mechanism.

On this note I must close. I hope I have succeeded in demonstrating

how the venerable Franck-Condon principle can continue to enlighten and

amuse us in application to a variety of bound-free coupling problems in diatomics.

332

REFERENCES

1. J. Tellinghuisen, J. Chem. Phys. ~, 2821 (1973).

2. G. Herzberg, Spectra of Diatomic Molecules (Van Nostrand, Princeton,

N. J., 1950), Chpt. 7.

3. J. Tellinghuisen, J. Chem. Phys. 2.,2., 849 (1973).

4. J. Tellinghuisen, et al., J. Chem. Phys . .22, 4473 (1976).

5. A. Tam, et al., Phys. Rev. Lett. E' 85 (1975).

6. B. Sayer, et al., J. Phys. B: Atom. MoIec , Phys. 1, L293 (1976).

7. R. Exton and W. Snow, private communication.

8. D. L. Rousseau and P. F. Williams, Phys. Rev. Lett. 22, 1368 (1974).

9. J. Tellinghuisen, Phys. Rev. Lett. 34, 1137 (1975).

10. R. S. Mulliken, J. Chem. Phys . .?2., 309 (1971).

11. J. Tellinghuisen, Chem. Phys. Lett. ~, 359 (1974).

12. J. E. Velazco and D. W. Setser, J. Chem. Phys. 62, 1990 (1975).

13. M. F. Golde, J. Mol. Spectrosc. ~, 261 (1975).

14. J. Tellinghuisen, to be published.

15. H. Scheingraber and C. R. Vidal, J. Chem. Phys. 66 (in press).

16. J. Tellinghuisen, et a l ,., to be published.

17. L. Brewer and J. Tellinghuisen, J. Chem. Phys. _§_§_, 3929 (1972).

18. J. Tellinghuisen, J. Chem. Phys. 57, 2397 (1972).

19. M. Broyer, et al., J. Chem. Phys. 64, 4793 (1976).

20. T. R. Govers, et al., Chem. Phys. 1,285 (1975).

21. A. J. Lorquet and J. C. Lorquet, Chem. Phys. Lett. l:i, 138 (1974).

22. J. Tellinghuisen and D. L. Albritton, Chern. Phy s , Lett.1.!., 91 (1975).

23. A. L. Roche and H. Lefebvre-Brion, Chem. Phys. Lett.~, 155(1975).

24. P. Erman, Phys. Scripta _!i, 51 (1976).

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