Calculation of Franck-Condon Factors

for Undergraduate Quantum Chemistry

Roland L. Dunbrack, Jr.1
Harvard University, Cambridge, MA 02138

Numerous theories exist for the calculation of potential sur- function and a potential and calculate eigenvalues and ei-
faces for diatomic and polyatomic molecules, and a number genfunctions. A set of functions is orthonormal on [a,6] if
of these have been presented in this JOURNAL for use in
undergraduate quantum chemistry courses (f, 2). It is use- <t>*(q)<t>j(q)dq
=
(2)
J
ful, however, for students to see how such computations are
used in relation to experimental data such as ultraviolet We wish to calculate the eigenvalues and eigenfunctions of
absorption and fluorescence intensities. One important step the following:
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

in such a comparison is to use the potential surfaces to

calculate vibrational wavefunctions and the transition prob- Hif>
=
E+ (3)
abilities between vibrational levels of two electronic states. where ft is the Hamiltonian of a one-dimensional system,
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The^e transition probabilities are proportional to the -h2

Franck-Condon factors (3), which are the squares of the A
d2
+ V(9) (4)
overlap integrals between vibrational wavefunctions, ^d,2
cmn«l[J- *gm*(<?hM<?)d<?]l2 (1) and E is the energy.
We use a variational method (6) to approximate ^ as a
where q is the coordinate of motion along the potential finite linear expansion in the orthonormal functions (pj
surface, 4/gm is the mth vibrational wavefunction of the
N~l
ground state, and \pM is the nth vibrational wavefunction of
an excited electronic state. The derivation of the Franck-
Condon factor formula in eq 1 is given in a number of stan-
'P
~

^
y-o
Cj<Pj (5)

dard quantum chemistry texts (4). We may explain eq 1 in a where the Cj are (in general) complex, ip is exact if N
-»
«>, but

qualitative way by stating that an electronic transition is we are looking for an approximation by keeping only a par-
more likely to occur when probable ground state nuclear tial sum.

configurations (i.e., large values for |i/'gm(g)l) coincide with The Cj are determined by finding the solutions to the
probable excited state nuclear configurations (large matrix equation (6)
i'/'xn(<?)l)- This is what is meant by vertical excitation: the HC =
EC (6)
nuclei have very little time to move during the excitation of
an electron, and thus the transition is more likely to occur where
when there is large overlap between the ground and excited
state vibrational motions. Hq
=
S (7)
There are several techniques used to calculate vibrational H is an NXNmatrix and C is an N-element column vector.
wavefunctions, some based on numerical methods such as The E’s and C’s can be found by diagonalizing the H matrix.
the Noumerov method (5). In this paper, we present a differ- The eigenvalues En and the eigenvectors Cn give approxi-
ent method, widely used for polyatomic molecules that can mate energies and wavefunctions for the N lowest levels of
be programmed by advanced undergraduates. The calcula- the potential V(g).
tion involves analytic representation of one-dimensional po- The difficulty lies in calculating the matrix elements H,j.
tentials, expansion of the wavefunctions in an orthonormal Ordinarily, we try to expand the potential V in the same
basis, and a simple computation of the Franck-Condon fac- orthonormal basis 0, as we used for the wavefunctions. In
tors between levels of different electronic states. A number most actual cases, only a few points of the potential are
of different assignments are possible, depending on the level known and we must make a least-squares fit or guess the
of students and the amount of time that the project is to coefficients in the expansion
consume. The calculations require that a digital computer M
with matrix diagonalization routines be made available to
the students. V(q) =
V,4i(q) (8)
(=0
We have used this assignment in an experimental physical
The key to choosing a basis is to make the integrals in eq 7
chemistry course taken by third- and fourth-year under-
graduates. We have found it successful in showing our un- easy to compute.
Once the eigenfunctions have been obtained, we can calcu-
dergraduates the usefulness of a computer in quantum
late the probability of a transition from a ground electronic
chemistry and in teaching them the concepts of eigenfunc- state level to an excited electronic state level by calculating
tion expansions of wavefunctions and the principles of spec-
the overlap integrals between the appropriate vibrational
troscopy.
wavefunctions. If
Theory
Many calculations of wavefunctions involve the use of Pgm
=
V bi<Pi (9)
orthonormal functions which are used to expand a wave-

=
Present address: University of Cambridge, Emmanuel College,
1
'Pgn
YJci‘t‘i
Cambridge CB2 3AP, England. i

Volume 63 Number 11 November 1986 953

 Table 1. Eigenvalues for Ground Stale Torsional Potential of dibromo ethylene wewould calculate the moment of inertia,
Tolane h, of the Br-C-Br group rotating about the C=C double
bond, and the moment of inertia, I% of the H-C-H group. We
Soa Exp.b Calc.c find the reduced moment of inertia in an analogous fashion
to finding reduced masses:
v =
0 0 0
V=
v=
1

2 32
17.1
33.8 1 = % (16)
v= 3 50.1
h + h
v =
4 66 66.0 If we write the energy in wavenumbers, and the moment of
81-4
5
inertia, I, in amu A2, then B is given by:
=
v
v= 6 96 96.3
v = 7 110.8 16.8641
B =
-;-cm (17)
v —
8 125 124.6
v —
9 137.9
v= 10 150 150.6 The wavefunctions are expressed in an orthonormal basis
v= 11 164 162.5 of rigid rotor functions (a Fourier series, with each term
v= 12 173 173.4 normalized). The wavefunctions of an even potential are
v= 13 183.0 either even or odd (but not mixed) so we can split the Fourier
v = 14 189 190.5 series into even and odd parts,
3
All levels are doubly degenerate. Even quanta eigenfunctions are cosine series, and
+ (l8)
odd quanta transitions are sine series. Each series is 50 terms long (i.e., N = 50)
b
All energies are in cm-1 and are relative to the lowest energy vibrational level.
Experimental energy levels are from ref 8.
(27t)1/2 ^^ C0S;T

c Calculated with B 0.379 cm-' and potentials given in the text and in ref 8.
—

v , b:
'Paid
=

Z ~1/2 SlnJ'T <19)

we have Consequently, two sets of wavefunctions must be calculated:

ZZ
or just the square of the complex dot product of B and
=
\B-CP
Imn
The Imn are called Franck-Condon factors and the un-
squared integral is called a Franck-Condon or overlap inte-
gral. The transition probabilities Pmn are proportional to the
Franck-Condon factors (4).
Application to Torsional Potentials
Perhaps the most common example of this method is the
calculation of wavefunctions and Franck-Condon factors for
periodic potentials (7). Usually such potentials are found in
molecules with internal rotations such as ethane and ethyl-
ene. For ethylene, we might have a potential of the form,
first, where the matrix H is calculated using the even basis
functions of eq 18; and second, where H is calculated with
the odd basis functions of eq 19. The integrals involved are
tabulated in the appendix.
b‘^l 0aa The program we ask our students to write calculates the
matrix elements and then diagonalizes the matrix H with a
packaged routine. Such routines are available on most col-
(10) lege and university mainframe computers and are also avail-
able for personal computers.2 The appropriate Franck-Con-
don factors are calculated and compared with experimental
C, absorption and fluorescence spectra.
(11) As an example, we calculate the energy levels and Franck-
Condon factors for tolane (1,2-diphenyl acetylene or Ph—
C=C—Ph). This molecule has a torsion mode in its ground
state (S0) and in an excited state (Si), that involve rotation
of the phenyl groups about the carbon-carbon triple-bond
axis. The technique of dispersed fluorescence spectroscopy
has been used by Okuyama, Hasegawa, Ito, and Mikami (8)
to determine the energy levels of these modes. The spectra
were obtained by focusing a tunable laser at the frequency of
a particular absorption band (v' = 1, 2, 3,4 in the notation of
ref 8) of the excited state, and dispersing the released light to
measure the frequencies and intensities of the fluorescence
down to the ground state levels (o 0,1, 2, 3, etc.). Okuyama
=

et al., using a similar procedure to the one described here,

(12) measured the torsional spacings of the So and Si states
V(r)=^(l-cos2r) through fluorescence, and fitted the spacings to potentials of
where r is the angle between the HCH planes.
the form of eq 12. For the ground state, they found that the
best fit was obtained when V0 202.0 cm-1. For the excited
=

V0 for the ground state of ethylene is ~65 kcal/mol. More

generally, the potential might be fit to a finite cosine series, state, the best fit was Vo 1600 cm^1, and the kinetic energy
=

constant B was taken as 0.379 cm^h With these potentials,

N
they calculated the Franck-Condon factors for the fluores-
V(r) =
V0 + V V„cos(nr) (13) cence transitions and compared them with the results of the
n=l
experimental spectra. Their calculated results are repro-
We can write the Hamiltonian as duced here using a program written for our experimental
physical chemistry course.
ft = -B A + V(r) (14) The eigenvalues for the ground state potential are summa-
rized in Table 1. For a potential with only one adjustable
where parameter, the agreement is quite good. With the eigenva-

(15)
2
Mathematical routines lor mainframes and personal computers
/ is the reduced moment of inertia for two groups rotating areavailable from 1MSL, NBC Building, 7500 Beliaire Boulevard,
about a common axis. That is, in a molecule such as 1,1- Houston, TX 77036.

954 Journal of Chemical Education

 Table 2. Intensities for the Dispersed Fluorescence Spectra of program that calculates eigenvalues, eigenvectors, and
Tolane Franck-Condon factors for torsional potentials such as 9-
phenyl anthracene and its derivatives (9, 10), biphenyl (11,
Si V3 So vb Exp. Int.c Calc. Int.a 12), ethylene (13) and toluene (14). In addition, other kinds
of potentials and basis sets for the wavefunctions can be
II
0.0 v= 0 0 1.00 1.00 1.00
used. For instance, for diatomics we can use one-dimension-
v=2 34 0.09 0.11 0.11
4 0.04 0.02 0.02
al potentials that are harmonic with cubic and quartic terms
v =
66
ir=6 97 0.004 0.004 added to account for anharmonicity. The wavefunctions for
= 1 48.9 V= 1 0 1.00 1.00 0.77
this kind of potential are linear combinations of harmonic
v= 3 33 0.35 0.34 0.26
oscillator functions, with the frequency of the oscillator tak-
v = 5 65 0.13 0.10 0.08 en to correspond to the harmonic term of the potential (6).
v= 7 95 0.04 0.03 0.02 A copy of the computer program used here to calculate
II N> 97.4 v=0 0 1.00 1.00 0.12 torsional wavefunctions is available from the author upon
v=2 34 3.26 3.60 0.42 request.
V = 4 65 2.64 2.87 0.33
v —
6 97 1.37 1.36 0.16 Acknowledgment
v= 8 121 0.69 0.57 0.07 I would like to thank Cynthia Friend for helpful com-
II co 145.4 v= 1 0 1.00 1.00 0.27 ments, and the Department of Chemistry, Harvard Univer-
v= 3 33 0.45 0.46 0.13 sity, for support of this work.
v= 5 65 1.17 1.04 0.28
v= 7 94 1.12 0.79 0.21 Literature Cited
v —
9 121 0.51 0.45 0.12 (1) Castano, F.; de Juan, J.; Martinez, E. J. Chem. Educ. 1983,60,91.
II
193.1 V= 0 0 1.00 1.00 0.02 (2) Cox, P. J. J. Chem. Educ. 1982,59, 275.
(3) (a) Franck, J. Trans. Faraday Soc. 1925, 21, 536. (b) Condon, E. U. Phys. Rev. 1926,
v=2 34 8.94 18.20 0.36 28, 1128; Phys. Rev. 1928,32, 858.
v = 4 66 0.61 0.14 0.003 (4) Steinfeld, J. I. “Molecules and Radiation”; Harper and Row: New York, 1974; p 118.
v= 6 97 6.11 7.40 0.15 (5) Blukis, U.; Howell, J. M. J. Chem. Educ. 1983,60, 207.
8 9.17 10.05 0.20 (6) Sims, J. S.; Ewing, G. E. J. Chem. Educ. 1979,56,546.
v —

125
(7) Lewis, J. D.; Malloy, T. B.; Chao, T. H.; Laane, J. J. Mol. Struct. 1972,12, 427.
(8) Okuyama, K.; Hasegawa, T.; Ito, M.; Mikami, N. J. Phys. Chem. 1984,88,1711.
Calculated frequency (in cm ’) of excited state torsion levels relative to lowest level. (9) Werst, D. W.; Gentry, W. R.; Barbara, P. F. J. Phys. Chem. 1985,89, 729.
N = 50. (10) Werst, D. W.; Londo, W. F.; Smith, J. L.; Barbara, P. F. Chem. Phys. Lett. 1985,118,
b
367.
Measured frequency (in cm-1) relative to lowest band of dispersed fluorescence for
(11) Murakami, J.; Ito, M.; Kaya, K. J. Chem. Phys. 1981, 74,6505.
given v* level. (12) Bastiansen, 0.; Samdal, S. J. Mol. Struct. 1985,128,115.
c
Intensities measured from ref 8, Figure 5, relative to lowest band. (13) Petrongolo, C.; Buenker, R. J.; Peyerimhoff, S. D. J. Chem. Phys. 1982, 76,3655.
a
Calculated Franck-Condon factors, using potentials described in text. First column (14) Murakami, J.; Ito, M.; Kaya, K. Chem. Phys. Lett. 1981,80, 203.
lists intensities relative to first band; second column lists intensities relative to origin band
(v' = 0 -* v = 0). Appendix
Integrals for torsional wavefunction calculations:
1) | cos(mr)dr =
0
lues and eigenvectors of both potentials in hand, we can
calculate the Franck-Condon factors and compare these re-
sults with the experimental intensities. The measured inten- 2) I sin(mr)dr = 0
sitities and calculated Franck-Condon factors are presented
in Table 2. The calculated Franck-Condon factors approxi-
mate the experimental intensities quite well for a crude one-
r. cos(mr)cos(nT-)dT
=
dimensional approximation. The one-dimensional poten- bmn

tials are able to reproduce even the large fluctuations in

intensity in the v' 3 and v' 4 fluorescence. The errors that
= =

do occur are due mostly to the crude approximation of the

potentials. In addition, there is the Condon approximation
IT i: sin(mr)sin(rer)dr =
Smn

of a vertical transition. Calculations involving non-Condon

effects are more difficult than the simple calculation de-
scribed here. i: COS(lr )cos(mr )cos(nr )dr =
%(Sl+mn + 5y_m| „)

Other Applications
+
r. sin(ir)cos(m7-)sin(n7-)dr
=
V2(5|„-([,m
A number of other molecules may be investigated using a

Volume 63 Number 11 November 1986 955