L. R.

Byers
University of Wisconsin A Teaching Aid for the Conceptualization
Madison, 53706

of the Franck-Condon Principle

In the last few years, photoelectron spectroscopy (PES)

has developed into a valuable tool for the experimental
chemist (1-3). One attribute of PES is the ease of under-
standing its elementary process—ionization. Although the
concept of ionization is introduced early, in an atomic con-
text, its natural extension to molecular systems is rarely
pursued. Ionization energies of monoatomic atoms are not
only difficult to obtain, but are also relatively uninteresting
in chemical discussions after being acquired. On the other
hand, the world of molecules viewed with the aid of PES is
beginning to show interesting and important chemical
trends heretofore obtained only with much greater effort
(4).
An informative example has been constructed in the ac-
companying illustration for the process
H2(i/' =
0) + hv —-
H2V =
0,1,2,..., 13) + e"
Even though this is the least complex molecular system, it
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

was chosen specifically to demonstrate features which

modern quantum mechanics and its application in the field
Downloaded via UNIV DE ALICANTE on April 13, 2023 at 15:51:55 (UTC).

of electronic spectral analysis required many years to for-

mulate, e.g. the Franck-Condon principle (5).
The appropriate energy curves (6) with their associated
vibrational energy levels, which are reproduced here, are
very accurately known from electronic band spectra and
are thus quantitative. Also drawn in for the v" = 0 level of
the ground state of Ha are the classical Franck-Condon
turning points and a qualitative picture (7) of the quan-
tum mechanical vibrational wavefunction (which is expect-
ed to be slightly skewed toward values of r > re due to the
asymmetry in the shape of the potential well). The inset
PES spectrum (8) for the ionization of H2 shows a plot of
signal intensity from the electron energy analyzer versus
the binding energy, a quantity derived from the electrons’
kinetic energy (9).
Qualitatively, a simultaneous comparison of the diagram
with the spectrum reveals three interesting points. First,
according to the Franck-Condon principle, the 1/ = 2 v"
=
0 transition might reasonably be expected to be the most
intense, in that a vertical transition from the most probable
internuclear separation in the ground state of H2 would rise
closest (shown by arrow) to this vibrationally excited level
in H>2+. This is indeed observed in the PES spectrum. Sec-
ond, and further, the general shape of the envelope (shown
by dotted line) in the spectrum is easily seen to be analo-
gous to the shape of the vibrational probability distribution
over r in the v" 0 level of H2. It should be mentioned that
=
the actual shape of this envelope is dependent upon transi-
tion probabilities between the various pairs of states (10),
but, the alteration in the envelope is qualitatively negligi-
ble. Third, the regular decrease in the spacings of the v' vi-
brational energy levels, due to anharmonicity, is readily ap-
Juxtaposition of the potential energy curves of Sharp (6) for H2 (12g+) and
H2+ (22g+) with the photoelectron spectrum of Siegbahn, et al. (8) for the
ionization: H2 (12g+) — H2+ (22g+).
parent. Numerical values for these differences may be
found in Siegbahn’s original spectrum (8).
Other examples, which may be constructed for ioniza-
tions of N2, NQ, and O2, are qualitatively similar, although
generally fewer v' vibrational levels are observed (11, 12).
It is hoped that this lucid illustration of a real molecular
system may be usefully employed in the understanding of
**-
the points discussed herein.
Literature Cited
(1) Bock, H., and Mollere, P. D„ J. CHEM. EDUC.. 51,506 (1974).
(2) DeKock, R. L.. and Lloyd, D. R., Advan. Inorg. Chem. Radiochem., 16,65 (1974).
(3) Brundle, C. R., and Robin, M. B., in “Determination of Organic Structures by Phys-
ical Methods,” (Editors: Nachod. F. C., and Zuckerman, J. J.), Vol. 3, Academic
Press, New York, 1971, pp. 1-71.
(4) Baker, A. D., Accts. Chem. Res., 3, 17 (1970).
(5) Herzberg, G., "Spectra of Diatomic Molecules,” 2nd Ed., D. Van Nostrand Co.,
Princeton, 1950, pp. 194-196.
(6) Redrawn from data of Sharp, T. E., Atomic Data. 2, 119 (1971).
(7) Ref. (5), pp. 93-94.
(8) Redrawn from illustration of Siegbahn, K., et al., "ESCA—Atomic, Molecular and
Solid State Structure Studied by Means of Electron Spectroscopy,” Almquist and
Wiksells, Uppsala, 1967, p. 209.
(9) Turner, D. W., Prnc. Roy. Soc., Ser. A., 307,15 (1968).
(10) Berkowitz, J., and Spohr, R., J. Electron Spectrosc.. 2, 143 (1973).
(11) Turner, D. W„ and May, D. P., J. Chem. Phys., 45, 471 (1966).
(12) Gilmore. F. R., J. Quant. Spectrosc. Radiat. Transfer, 5, 369 (1965).

+ + +

790 / Journal of Chemical Education