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Use Of Matrix Methods In The Calculation Of The Normal Modes Of Molecular

Vibrations And Refinement Of Molecular Force Fields

Conference Paper · December 1981

DOI: 10.1117/12.932059

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Vasudevan Lakshminarayanan
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 Use of matrix methods in the calculation of the normal
Use of normal modes
modes ofof
molecular vibrations and
and refinement of molecular force fields

Vasudevan Lakshminarayanan
Department of Physiological Optics, School of
Optics, School of Optometry
University of
University of California,
California, Berkeley,
Berkeley, California
California 94720
94720

Abstract

In
In this
this article
article the
the various
various matrices
matrices and
and matrix
matrix operations
operations used in
in the analysis
analysis of vibra-
vibra-
tional spectra of
tional of polyatomic molecules
molecules are
are described.
described. This to the
This is applied to the quantitative
quantitative
refinement
refinement of
of molecular force
force fields
fields for
for Wilson
Wilson GG-F
-F calculations
calculations and
and criteria are developed
satisfied by
which must be satisfied by an
an acceptable
acceptable force
force field.
field. This
This method permits an
an unambiguous
choice
choice between
between different force fields
different force fields which predict
predict the observed frequencies
frequencies but
but give
give dif-
ferent
ferent potential
potential energy
energy distributions amongst
amongst the various internal
internal coordinates.
coordinates.
Introduction

The
The calculation
calculation of the normal modes of vibration of a large
of the large molecule has
has traditionally
traditionally
been hampered by a lack of criteria for for checking thethe validity of of the
the calculated
calculated normal
normal mode
mode
displacements. Generally only a a comparison
comparison of of the
the calculated
calculated normal
normal mode
mode frequencies
frequencies with
with
infrared and
observed infrared and Raman
Raman spectra
spectra are
are available.
available. A largelarge molecule ofof low
low symmetry
symmetry will
will
3N-6-6 vibrational
have 3N vibrational frequencies
frequencies (N(N being
being the
the number
number ofof atoms)
atoms) while force
while the number of force
constants
constants which
which must
must be
be evaluated
evaluated isis much larger
larger (for
(for aa generalized valence force field it
is (3N
(3N-6) (3N-5)/2).
-6) (3N- 5)/2). Thus several sets
Thus several sets of
of force
force constants (i.e.,
(i.e., force
force fields)
fields) exist which
give
give essentially
essentially thethe same set of
same set of observed frequencies but different eigenvectors,
observed frequencies eigenvectors, i.e.,
i.e.,
sets of
different sets of atomic
atomic displacements.
displacements. SinceSince the
the assignment of a molecular vibration is
essentially
essentially an an assignment
assignment ofof atomic
atomic displacements vibration, an error in
displacements involved in the vibration,
these
these eigenvectors
eigenvectors actually
actually renders
renders the
the calculation
calculation essentially useless.
useless. The indetermina-
cy
cy in
in the
the force
force field
field of
of large
large molecules
molecules is is even
even more serious if
more serious if one does not transfer
approximate force
approximate force constants from smaller
smaller molecules,
molecules, so so as to
to make assignments
assignments from
from molecule
molecule
to
to molecule consistent. Isotopic substitution is
Isotopic substitution is aa valuable method for
for checking the
validity ofof the
the choice
choice of force constants sincesince this is is a method ofof changing
changing the
the atomic
atomic
masses without changing
changing the
the force
force constants
constants so so that
that in
in principle
principle another
another set
setofof3N3N-6
-6
frequencies
frequencies areare available forfor each
each isotopic
isotopic substitution.
substitution. In In practice for
for large
large molecules
molecules
many of
of whose
whose normal
normal modes involve rather complicated simultaneous
simultaneous displacements
displacements of of all
all
of the
of the atoms, the changes in frequency observed upon isotopic
atoms, the isotopic substitution
substitution isis so
so small
small
as to
as to lie
lie within
within the
the error of calculated frequencies and may not provide provide sufficient
sufficient infor-
infor-
mation for determination of of the
the force
force field.
field.

It
It has
has been
been shown
shown from
from the
the theory
theory of
of the
the resonance
resonance Raman effect (RRE)
Raman effect (RRE) that
that the
the totally
symmetric
symmetric modes
modes which
which are
are active in the
active in the RRE
RRE derive their intensity from
derive their from the
the displacement
displacement of
the
the nuclear
nuclear geometry
geometry of
of the
the molecule in going from the ground electronic state
molecule in state to
to the
the excited
excited
(resonant) electronic state.
(resonant) state. If the
If the shift in the
shift in the nuclear
nuclear geometry isis small
small as
as it
it may
reasonably
reasonably bebe expected in a
expected in a large
large molecule
molecule with oneeelectron
one e electron excitation,
excitation, then
then the
the dependence
dependence
of
of the
the RRE
RRE upon
upon the
the shift in the
shift in the electronic
electronic state
state A,
A. along the jth
j normal coordinate
coordinate is
is 1-3
1 -3

-1 (Aj)2
I. < WL) aa (A*) 2 , 2 f((E r el _- K)
( eo - H» L ) 2 + r 2jr> WL)2
2 ++ rj?-
F31 1 = K (A*)
K 2 Q.
02 (i)
I. (wL) (Aj)2 qj [ Eeo - WL)2 + r2i PE (1)

tt^ is
where Q. is the circular frequency of of the
the jjth normal
normal mode,
mode, EEee
eo and Eel
E e ]^ are
are the
the zeroth
zeroth and
and
first vibrational
first vibrational levellevel of
of the
the e^Jl (resonant) electronic
e- (resonant) electronic state
state and
and CL
w-^ isis the
the circular
circular fre-
fre-
quency ofof the incident light
light and
and r is is the
the damping
damping or
or linewidth
linewidth ofof each of of the vibrational
vibrational
levels (which are assumed to
levels to be
be equal).
equal). K is is a constant for
for aa given
given incident
incident exciting
exciting fre-
fre-
quency 5L.
0)^. From
From aa measurement
measurement ofof Ij
I-: versus w,. (such a curve is
wL (such is called
called an an RRE
RRE excitation
excitation
profile),
profile), A. A 6: can be obtained.
obtained. Even if if the displacements Aj Aj are large
large andand egn.(1)
eqn.(l) is
is only
only
approximately correct,
approximately correct, still
still the excited state
the excited state shift
shift can be obtained fromfrom aa measurement of
profile.
the excitation profile.
In this
In this article
article it
it will
will be
be shown
shown how the
the vibrational calculated using
vibrational frequencies can be calculated
techniques and how the experimental
matrix techniques experimental resonance
resonance Raman
Raman intensities
intensities can
can be
be used
used to
to
analyze the
analyze the resultant
resultant eigenvectors and lead to a method for resolving the
eigenvectors and the indeterminancy
indeterminancy inin
normal coordinate
coordinate problems.
problems. This
This method in detail elsewhere3
method has been published in elsewhere 3 and
and has
has
been successfully applied
been successfully applied inin the
the case
case of
of methyl
methyl uracil to obtain its
its force
force field
field and
and the
the
excited state molecular geometry.
geometry.

300 //SPIE
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 of molecular vibrational frequencies and displacements
Calculation of

Normally when
Normally one discusses the calculation of molecular vibrational frequencies
when one frequencies in
in any
any
of the standard treatments4 "-6
of the 6 one
one discusses
discusses setting
setting up
up the
the Wilson
Wilson GG and
and FF matrices and ob-
matrices and ob-
taining the
taining the eigenvectors and
and eigenvalues
eigenvalues of
of the
the product
product of
of these
these matrices.
matrices. In
In this
this section
the two
the two main
main methods
methods for
for obtaining the
the normal
normal modes
modes of
of vibrations
vibrations ofof molecules using matrix
matrix
be discussed.
techniques will be discussed.
For small
For small molecules
molecules with high symmetry the setting up of of G and F matrices 7 is
,F matrices7 is the
the method
of
of choice
choice since
since they
they can
can be
be blocked
blocked byby the
the use
use of symmetry and
of symmetry and deal
deal with small
small matrices in in
which
which case
case further
further restrictions
restrictions cancan be
be placed
placed inin the
the possible
possible values
values ofof the force constants.
constants.
However
However for
for large
large molecules
molecules itit isis almost
almost always
always necessary
necessary toto solve
solve virtually the entire
entire
eigenvalue problem
problem atat once.
once. If
If this
this is
is done on a computer the GF
done on GF method hashas the
the disadvan-
disadvan-
tage that the
tage that the product matrix is is unsymmetric
unsymmetric and
and consequently
consequently difficult
difficult to to diagonalize.
diagonalize. A
better
better method
method isis to
to use
use the
the Wilson
Wilson BB matrices
matrices andand to
to form the force constant
the force constant matrix in in mass
mass
reduced coordinates. This is a simple calculation that that lends itself easily to to computer
computer
techniques. A difficulty which occurs comes from the transformation from from the
the set
set of
of Carte-
sian displacement coordinates,
sian coordinates, aa 3N 3N dimensional
dimensional vector
vector to
to the
the set
set of
of internal
internal coordinates,
coordinates,
usually aa 3N
usually 3N-6
-6 dimensional vector. The transformation matrix for aa nonlinear molecule must
dimensional vector. must
necessarily
necessarily be a nonsquare matrix. As long long as the number of internal
internal coordinates
coordinates equals
equals
3N-6 , the
3N -6, thenumber
number of
of normal
normal coordinates,
coordinates, thethe rectangular
rectangular BB matrices
matrices havehave inverses
inverses asas do
do their
their
transposes
transposes and
and these
these can
can be
be used
used toto elucidate
elucidate very
very quickly and simply the nature of
quickly and of the
the cal-
cal-
culation. Some
Some of
of the computational methods given hgre here are implicit
implicit in in the
the rather meticu-
lously detailed
lously detailed computer programs of of Schactschneider
Schactschneider . In
In the
the following treatment we will
.

always assume thethe case

case of
of 3N
3N-6
-6 internal
internal coordinates with no no redundancies.
redundancies . The use of of sym-
sym-
considerations has
metry considerations has been
been expressly
expressly eliminated
eliminatedeither
eitherasas aa characterization
characterization of of the normal
modes or as a blocking out of the the corresponding
corresponding matrix equations
equations since
since this
this has
has been
been very
very
well discussed in many books on group group theory
theory as as well spectroscopy4 > " ' ^ .
well as vibrational spectroscopy4,6,9
Consider a
Consider a molecule
molecule ofof N atoms held in rigid equilibrium position by valence bonds. bonds. At
equilibrium
equilibrium position
position there
there will
will be
be 3N Cartesian
Cartesian coordinates
coordinates which give give the position ofof each
each
atom. We the column
We now define the column vector
vector XX == (xl,x2,x3,
(x-L,X2,X3, .... - Xx3N)T
3]^) as the vector ofof all
all the
the
Cartesian
Cartesian displacement
displacement coordinates
coordinates from positions
positions ofof miminum
miminum potential energy. Note that
potential energy.
x-pX 2 ,x 3 belong to
xl,x2,x3 to the
the first
first atom,
atom, x4,x5,x6
x 4 ,x 5 ,Xg to
to the
the second
second atom,
atom, etc.
etc. The equilibrium posi-
posi-
tion
tion ofof the
the ground
ground state is given
state is given by
by the
the equation
equation XX == 00 which implies that
which implies that none
none of
of the
the
atoms
atoms are
are displaced along anyany of
of the
the 3N3N displacement
displacement coordinates.
coordinates. The The kinetic energy for
for
all
all of
of the
the atoms
atoms including
including the
the three
three translations
translations and and three
three rotations about the
rotations about the molecule
molecule
coordinate axes and and the
the 3N
3N-6
-6 vibrations
vibrations can can be
be given by

N .22
. . T .
T= 2 E
i=1
MiXi
M.X.
i i
= 22 X
± M X (2)
(2)
i=1

where T is
where is thethe kinetic energy, energy, Mi
M^ is
is the mass of the atom corresponding to
to the
the ith
i Cartesian
Cartesian
displacement coordinate with
displacement
.T
.T . .

X == (x1,x2,x3,
( X]L ,x 2 ,x 3 ,. . . . . XSN)
x3N)
(3)
M == Diag (M1,M2,
(M 1 ,M 2 , .... .M 3N )
M3N)
The corresponding
The corresponding potential
potential energy is
is given by

V =
= |-1 XT
XT FX
Fx X (4)

where Fi
F?. is
is a force constant
constant matrix
matrix element
element in
in XX coordinates.
coordinates. This may be regarded as
as the
the
contribution to
contribution to the
the potential for a unit
potential energy for unit displacement
displacement of the corresponding atoms
atoms
X^ and
along Xi and X..
X..
As
As aa first
first step
step in
in setting
setting up
up the
the Hamiltonian so that
Hamiltonian so that it
it will
will be easier to diagonalize
diagonalize in
in
terms of
terms of normal
normal modes it is
modes it is useful
useful to make a coordinate transformation from
from Cartesian to
mass reduced Cartesian displacement
displacement coordinates.
coordinates. The relationship between the two
two is
is given
by

qqi
± ==Mi
/IT xi
X:L or
or g=
q = M`
M^ X
X (5)

with
with this
this transformation
transformation the total Hamiltonian is just
the total just
2H = qT q + qT Fq q
qT Fq (6)
(6)

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 Fq =
= M a
* FX
Fx M * (7)
(7)

Before introducing the important

Before important and necessary concept of internal
internal coordinates
coordinates in
in which
the actual
the actual force
force field
field of
of the
the molecule
molecule must
must be expressed, let
be expressed, let us first
first show how easy it
it is
is
coordinates. To do this we must
to obtain the normal coordinates. must solve the eigenvalue equation
Fq AA =
= A AA_ (8)
(8)

where
where _AA is
is the
the diagonal matrix
A. = Diag (al,A2,
A ( A-p X 2 , . . . . . AAN)
N) (9)
(9)
.th
where Xi Aj is
is the
the square of
of the circular frequency Qi flj of
of the
the j normal
normal mode ofof vibration of of
the
the molecule. Six
Six of
of the A's will
the As will be
be zero
zero since
since they
they correspond
correspond to
to combinations
combinations of
of rota-
rota-
tions
tions andand translations
translations of
of the
the molecule
molecule asas aa whole
whole and
and A is
is the
the matrix ofof the eigenvectors
F q . Since F^
of Fq. symmetric, it
Fq is symmetric, it has orthogonal eigenvectors
eigenvectors which means thatthat AA is
is also
also
orthogonal. If we
If we right
right multiply both sides of eqn.(8)
eqn.(8) by AT A/ we get
get
AT
AT FFq
q A =
= A_
A (10)
if the following transformation is
Now if is made
qq == A Q (11)
normal coordinates Q,
to normal as
Q, we get the total Hamiltonian as
2H = QT Q + QT AT Fq
Fq A Q (12)
or in view of eqn
or eqn (10)
(10)
QT Q + QT A Q
2H == QT QT A (13)
Equation (13) can
Equation (13) can be
be written as
6
6 '2 3N '2 22
2H == E Q.Q. + E (Q.
EN ( QZ ++ Q.
ft. Q.)
Q2 ) (14)
(14)
jj=1
= l JJ j=7
j=7 J
J J
J JJ
where the first
where the first six
six normal coordinates which have zero frequencies
frequencies are
are linear
linear combinations
combinations
of translations and
of and rotations
rotations about
about the
the three
three molecular
molecular axes.
axes.
If we
If we wish
wish to
to know for
for a given
given normal
normal mode
mode Q.
Q. with fij what the
w+th frequency Qj the displacements
are,
are, we
we use
use the
the fact
fact that
that the
the inverse
inverse of
of A^
A is J A'
is J A/ to obtain from
from egn.(11)
eqn.(11)
T
Q = E A M2 Mk (15)
k
Xk

Thus for any

Thus for any given
given normal
normal mode we can get the corresponding displacement.
displacement.
For the establishment of a suitable
For suitable force
force field,
field, it
it is
is absolutely
absolutely necessary
necessary to
to introduce
introduce
the concept
the concept of
of internal
internal coordinates
coordinates due
due originally
originally to
to Wilson10.
Wilson 10 . The coordinates
The internal coordinates
R are
are related
related to
to XX by the linear
by the linear but
but nonsquare transformation
R = B X (16)
The internal coordinates
The internal consist of
coordinates consist of bond stretches,
stretches, angle bends,
bends, torsional
torsional motion,
motion, out
out of
of
place wags,
wags, etc.
etc. To each internal
internal coordinate there will be aa force
force constant.
constant. These force
force
constants may be transferred fromfrom one
one molecule
molecule to
to another.
another. There is
is no comparable
comparable way
way of
of
such aa transfer
making such transfer in
in Cartesian
Cartesian coordinates.
coordinates. The potential energy in in terms
terms of
of internal
internal
is
coordinates is

2V = RT
RT F R = £E Fik
F ik Ri
R i Rk
RR (17)
ik

where
where FF is
is the
the force
force constant
constant matrix in terms of
of internal coordinates.
coordinates. In terms of
In of the Fq
Fq
we get
matrix we get
2V = qT
T MM* BT F B MM~*
a q (18)
from which

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 Fq ==M ~Z2 BT
Fq BM
F B
BT F M 22 (19)

When the number

When the of atoms
number of in the molecule gets progressively larger,
in the difference between
larger, the
will
space will
R space and X space get smaller. If
get smaller. are redundancies R space
there are
If there ultimately
can ultimately
space can
become larger
become larger than the X space. When
space. that happens
When that and when
happens and F^ matrix
one diagonalizes the Fq
when one matrix
as calculated from
as calculated the FF
from the matrix by
matrix means of
by means one finds
egn.(19), one
of eqn.(19), finds simply an additional zero
additional zero
for every
for every redundancy.

traditional way
The traditional
The of solving the molecular
way of is to set up the
molecular eigenvalue equation is
terms of
in terms
Hamiltonian in internal coordinates.
the internal
of the we have
since we
coordinates. To do this since potential
the potential
have the
energy, we
energy, need to
only need
we only up the
set up
to set energy as
kinetic energy
the kinetic as
•m • -m _-| rp i JL _T
2T = q1 q
qT = R 1 (B -1)T
RT ) MZ M 2 B -1 R
M 2 MZ R (20)

it is
where it
where that even though B is
is assumed that and its
matrix, both B and
is a nonsquare matrix, transpose will
its transpose
have an inverse. In the
inverse. In the appendix will be
this will
appendix this be shown fact
shown to be true and using the fact
-IT
1)T T -1
(BT)
(B V
(B = (B 1 ) -1 (21)

we may write

2T = RT [(BT) -1 M (B'-1)]
1 )] R
R (22)
~
and
and define the matrix GG -1 as
the matrix
-11 (BT) -1 "1
-1
M (B) (23)

so that
so is called
which is
that GG which the inverse
called the kinetic energy matrix is defined by
inverse kinetic
T
G = B MM -1 BBT1 (24)

total Hamiltonian
The total
The is therefore
Hamiltonian is
' T -1 ' T
2H == R 1 G R + R RT F R + + (25)

The relationship between

The relationship between the internal is given by
normal coordinates is
internal coordinates and the normal
the
the transformation

R = L Q (26)

Putting eqn.(26) in
Putting eqn.(26) eqn.(25)
in eqn.(25)
*T T 1 * T T
2H -= QQT LT
L G-1
G L Q ++ Q L F L Q
QT LT (27)

eqn.(13) we
Comparing with egn.(13)
Comparing get
we get
T -l
L GG -1 L = !_I
LT (28)
T
L F LL = ,A_
LT A (29)

from which we
from which we get result
known result
get the well known

G F L = LA
L A (30)

The L matrix may bebe considered the matrix

considered the by the
formed by
matrix formed right-handed
the right- handed eigenvectors of the
unsymmetric matrix
unsymmetric matrix GG F.
F. It
It should be that the vibrational assignment of Cartesian
be noted that
displacements in
displacements in aa normal
normal mode inverse L matrix and
mode involves both the inverse matrix.
the B matrix.
and the The B
matrix is
matrix is derived only from
from the molecular geometry
the molecular the LL"-1
but the
geometry but involves the
1 involves constant
the force constant
matrix. For calculations it
For small molecule calculations is apparent
it is even though
that even
apparent that is unsymmetric
though GG FF is
obtaining its
obtaining its eigenvectors
eigenvectors by solution of of the characteristic equation will be much easier easier
in the
in small space
the small coordinates.
of internal coordinates.
space of This is particularly true for medium and
This is small
and small
sized molecules
sized molecules with
with high symmetry so
high symmetry that the
so that can be
matrices can
the matrices be blocked off into vibrations
blocked off vibrations
which do
representations which
irreproducible representations
belonging to different irreproducible do not with one
interact with
not interact another.
one another.
But for
But for large molecules where this has to beldone
large molecules computer, it
on a computer,
be done on necessary to
is necessary
it is sym-
to sym-
metrize the
metrize the GF
GF matrix
matrix product
product by some method
method requires additional
which requires time.
computer time.
additional computer It
is seen
is seen that
that for
for large molecules of
large molecules low symmetry
of low the Fq
symmetry the efficient
diagonalization is more efficient
Fq diagonalization
since
since for
for aa modern
modern computer
computer with a large memory storage it it is easier to to work inin the 3N di-
the 3N
mensional space of mass reduced
mensional coordinates.
reduced coordinates.

Let us now obtain the

now obtain matrixininq-q-space.
the LL matrix space. eqn.(6) we
From eqn.(6) that T is
we see that in
diagonal in
is diagonal
and if
coordinates and
mass reduced coordinates diagonalize Fq
we diagonalize
if we Hamiltonian is
the Hamiltonian
F^ the diagonalized. Therefore
is diagonalized.

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 we have

Fq
Fg A =
= (M~*
( M 2 BT FF BBA.R 2) A
M~*) = A A_
A (31)
(31)

or
AT MM~* BT FF BB MM~*
2 BT A
-2 A = A_
A (32)

From which
which we see on comparison with
we see with eqn.(29)
eqn.(29)
L = M~* AA
B M-2 (33)
(33)

The
The LL matrix
matrix of eqn.(33) is
of eqn.(33) is of
of dimension
dimension 3N
3N-6
-6 by
by 3N,
3N, whereas
whereas the
the size
size of
of the
the L matrix in
in
eqn.(29) is (3N
egn.(29) is (3N-6) 2 . Since
-6)2. Since AT directly
directly gives the mass reduced atomic displacements the the X
space displacements are
space

X == M~* q
M-2 =
= M -1 AT
M~* AT Q (34)
T
AT
A the
the inverse of A contains
contains 66 zero
zero eigenvalues
eigenvalues for
for the
the nonharmonic motions and
and as
as many
other zeros as there are
other are redundancies
redundancies in
in internal
internal coordinates.
coordinates.
Hence we have seen in this section
section the
the various matrix equations
equations used
used in
in calculating
calculating the
the
of molecules.
vibrations of molecules. The
The discussion
discussion on actually setting up the G,F,B etc
on actually etc. matrices for
for
real system is
a real is beyond the
the scope
scope of
of this
this article
article and
and can
can be
be found
found elsewhere.`),5
elsewhere. > 5
Refinement of molecular
Refinement of molecular force fields
In
In this
this section
section aa method is developed
method is for the
developed for the quantitative refinement of molecular force force
fields for
fields for Wilson GG-F
-F calculations
calculations through
through the
the use
use of
of molecular
molecular orbital
orbital calculations of the the
bond
bond order
order changes
changes between
between resonant
resonant excited electronic state and the the ground
ground state
state together
together
with the
the observed intensity
intensity of
of the
the resonant
resonant Raman
Raman Spectrum.
Spectrum. Using thisthis method it
it is
is possi-
possi-
ble
ble to
to obtain
obtain the
the geometry
geometry of the molecule in
of the in the excited state since
since the
the intensity
intensity of
of the
the
normal
normal mode
mode of
of vibration
vibration which appears
appears in the spectrum is is directly related to to the
the change
change in in
geometry
geometry a molecule undergoes uponupon excitation
excitation toto an
an excited
excited electronic
electronic statel,2,12
state-'->2,12-16
-16 B if
If
we
we assume
assume that
that the
the electronic and
and vibrational
vibrational wave functions are separable
separable and
and changes
changes in in
excited
excited state geometry are are small
small then
then we
we can
can show
show that
that the
the Franck
Franck-Condon are
-Condon overlaps are
simply proportional
simply proportional to
to the shift in
the shift in potential minimum A! A? for the jth
j^^ normal
normal mode
mode in
in the
the
excited state.
state.
Consider
Consider aa molecule sent into an excited electronic state
molecule sent state with the
the resulting
resulting equilibrium
equilibrium
geometry
geometry expressed
expressed as
as aa series
series of
of displacements Xe displacement coordi-
Xe along the Cartesian displacement coordi-
nates
nates of
of the
the ground
ground state
state with
with corresponding shifts Re and _AAe
e in
in internal
internal and
and normal
normal coordi-
coordi-
nates respectively. We can use equations
equations (16)
(16) and
and (26)
(26) and
and write
Ae
Ae = IT 1 Re
L -1 Re (35)
(35)
A6
Ae == L-1
IT 1 B Xe
Xe (36)
If there
If there were
were no
no changes in vibrational frequencies inin the
the excited
excited electronic
electronic state
state then
then
it
it can
can be that the
be shown that the Franck
Franck-Condon
-Condon factors of the
factors in each of the 3N
3N-6
-6 normal
normal modes
modes are a func-
tion
tion of
of the
the displacement
displacement AlA^ only
only with
with
lim r f<l|v>.
lim <v|o>."l
<liv >. <vio >. = 0
0 (37)
AAee +} OQ L J JJ 7

It e is a zero element of the vector _A e then the corresponding frequency

It follows
follows that
that if
if Aj
A is a zero element of the vector Ae then the corresponding frequency
ft.
Q. will
will not
not be in the
be found in the spectrum
spectrum andand if
if Ae
A^ is
is large,
large, then
then the
the frequency
frequency S2j ftj will have aa
strong
strong intensity
intensity in the resonant Raman Raman spectrum.
spectrum. This can be seen seen from
from equation
equation (1).(1). On
the
the other
other hand
hand if
if there
there are
are vibrational frequency changes
vibrational frequency changes in going from
from the
the ground
ground to to the
the
excited
excited state
state there will be an an additional
additional change
change inin the
the Franck
Franck-Condon
-Condon factors.
factors. In In order
order to
see
see how
how large
large this
this effect
effect might
might bebe one has to
one has to evaluate the integral <1e <l e /0
/0 >.
>. for
for aa shift
shift A ee
and
and aa change in frequency Stj
change in ft. to
to ftQ.. This isis given by by g J

<le /Og >J

)(j[2 (38)

ft is
where IT is the
the arithmetic
arithmetic mean
mean of
of ftQ and
and Qft^. If ft == Qe
ft 0 we
. get the original approximation
we get
52 approximation ofof
no
no change in in excited
excited state
state frequency'
frequency^> 2 ,lb . From this it
,2,16 it is
is found,
found, for
for example,
example, that
that for
for
the
the same
same shift
shift AjAe if
if the
the excited state vibrational
excited state vibrational frequency is 80% of the the ground
ground state
state
frequency,
frequency, thethe measured
measured Raman intensity will
Raman intensity increase by 10% only.
will increase only. If
If the change
the frequency change
is
is large
large the
the normal
normal mode
mode structure
structure in in the excited state
the excited state isis probably very different andand a
detailed excited
detailed excited state potential curve would be required to to describe the
the Raman
Raman effect.
effect.

304 //SPIE
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 From this
From this we that if
we conclude that if A is small
is small the
the effect
effect of
of frequency changes will also be
be
small.
Using
Using molecular
molecular orbital
orbital theory it it is possible to calculate the bond order for for aa given
molecular system
system and
and we
we can
can assume
assume thethe following
following relation
relation between
between bond
bond length
length.ers
£m g and bond
order
order bm
brss (the
(the superscript
superscript refers
refers to to the
the mill
mth electronic state and
electronic state and the
the subscript
subscript refers
refers to
to
the
the bond
bond between and s)17,18_
between atoms r and s) 17 > 18 .
m D1"
m
- C, brs
"rs = CO
"0 - C1
"1 rs (39)
Qrs
T JT -j rj -i Q O
The values
values ofof the constants COCQ and
and C1
C-^ can
can be found
found in
in the
the literaturel5,17,18,3
literature. ' ' ' The
The change
change
in
in bond length (A
bond length (A£)p s in
2.4s in going
going from
from ground
ground to
to excited
excited state
state is
is linearly
linearly proportional
proportional toto
(Ab)p s , the corresponding change
(Ab)e s, change in
in bond
bond order,
order, and
and corresponding
corresponding toto each
each bond
bond rr-s
-s between
atoms
atoms rr and s will be an
and s an internal
internal bond
bond stretching
stretching coordinate
coordinate Rk.
R^. So
e
== (Ab) e
-C-, (ab)rs -C1 bbe (40)
Rk -C1 'rs =
"1 bk
"k
Putting this in
in equation
equation (35)
(35)

4
A 6 ==
J
E Ljk
Jk (-C1 bled
-! (41)
k
and the
and the intensity
intensity of
of the mode is
is given by
2
I. == K Cl
I. C (E
(z L;k
L- bk) Q. (42)
k

can get
from which we can get
2 2
Ìj = (k LJk bk S2j) (k Llk bk 1) (43)
1

where we have scaled thethe intensities

intensities of
of 3N
3N-7
-7 modes
modes which
which are
are weak
weak to
to the of the
the intensity of
strongest observed vibration in
strongest in the
the resonant
resonant Raman
Raman spectrum.
spectrum. Since I. I. = 0 for
for almost
almost all
all
but
but aa few
few symmetric
symmetric modes in an
modes in an actual
actual spectrum the ratios are small.°
small. Experimentally one
should be
should be able
able to
to observe
observe a band I.I- which is 10% or or more of
of II-,. Therefore itit is
is suggested
suggested
.

that any
that any force
force field
field leading to L^-
LA° be considered unacceptable if if the right hand
hand side
side of
eqn.(43)
eqn.(43) isis greater
greater than 0.1 for
than 0.1 for modes inactive in the resonant
resonant Raman spectrum.
spectrum. We get the
We get
inequality
2
( E L-1 be)
jk SZ2
k < 0.1 n ?1 (44)
2 2
Q.
(E L bk)
k Ik
lk *

if the shifts A.
Even if A. are large
large and
and egn.(1)
eqn.(l) is
is not
not exactly
exactly correct
correct still
still the
the inequality
inequality must
for modes inactive
be applicable for inactive inin the
the resonant
resonant Raman
Raman spectrui19t49ugh
spectrum though L3A^ must still
still be
be de-
de-
termined from
termined from an
an excitation
excitation profile
profile asas given
given in
in the
the literature
literature '41.. It should be
It be pointed
pointed
out that
out that the
the above
above sums over k are
are only approximately
approximately correct
correct since
since they
they are
are only
only over
over the
the
coordinates. The complete
M bond stretching coordinates. complete sums
sums must
must incorporate
incorporatethe
theother
other3N3N-6-M
-6 -M remain-
ing
ing internal coordinates. The The equations above assume
equations above assume that
that these other terms may be neglect-
neglect-
ed, and
ed, and this
this is
is valid for conjugated molecules which when excitedexcited to
to aa low
low lying
lying electronic
electronic
size and
state change their size and not
not appreciably
appreciably their
their shape.
shape. The complete sums are given by
M 3N ~ 6 -1
3N-6
Aee1 =
= LL.-11 bk
-C
e
be }
( )+E E L
71
R
e
(45)
J
° 1 k=1
k=1 Jk k k=M+l
k=M+1
Rk

A.e are usually obtained

The shifts A. obtained as as aa dimensionless
dimensionless parameter experimentally 1 . In
parameter experimentally1. In
order to maintain dimenisional
order dimensional equality
equality the the left
left hand
hand side
side of
of equations (35) and (36)
equations (35) (36) must
be multiplied by (0/SQj)z and
be and evaluating
evaluating the the constants
constants we
we arrive
arrive at
at the
the formula

z
Re =
= 4.46
4.46 xx 10
10-3 E LiJ (±
(+ 4) (1/v) (46)
J

where
where we have used
we have the fact
used the fact that
that

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 Re== LLA6
R6 Ae (47)
(47)

-1 th
v.* is the frequency in
The quantity v. cm -1 of
in cm the jjth mode
of the and if
mode and if A. is not
0e is available, we can
not available,
use egn.(l) as
use eqn.(l) an approximation
as an to obtain
approximation to obtain

z
Re == K z L.
KZ L ±J (Ij/vj) (±1);
(±1)j (48)
i
j
J

Varying the
Varying force constants until a good fit to the observed it
the force ir and Raman frequencies
and Raman is
frequencies is
obtained is the
obtained is the standard way of refining force
of refining fields.
force fields. It is suggested that
It is addition aa
in addition
that in
good fit
good to equations (43)
fit to and (44)
(43) and for all
(44) for the 3N
all the -6 modes
3N-6 also be
should also
modes should got since essen-
be got
tially these
tially these two
two equations give the
equations give the criteria for the eigenvectors in
criteria for in addition the
to the
addition to
experimentally observed.
eigenvalues which are experimentally
eigenvalues Additional information is
observed. Additional if data
got if
is got is
data is
for isotopic derivatives. Therefore only those force
available for
available fields which
force fields obey the
which obey con-
the con-
given above as well as give aa good
ditions given
ditions frequency fit
good frequency be considered
should be
fit should reliable.
considered reliable.
The above
The treatment gives a method for calculating the
above treatment Raman intensities
the resonance Raman for
intensities for
all the
all 3N -6vibrations,
the 3N-6 any force
and any
vibrations, and considered should
field considered
force field only obey the criterion
not only
should not
given above
given above but also correctly
but also predict which modes are resonant Raman active
correctly predict active (i.e., give
(i.e., give
intensities). The application of this method to ring system,
to aa planar ring Methyl Uracil,
system, Methyl has
Uracil, has
published. 3
recently been published.3
recently
Appendix
Here will be
it will
Here it shown how to B~-1 which
calculate B which isis used in the transformation from R
used in
space.
space to XX space. is aa
Since B is rectangular matrix
rectangul_arl of size
matrix of 3N -6 by
size 3N-6 3N, it
by 3N, two
will have two
it will
inverses. Let the
Let left inverse
left of B be B and by definition
and by

B-1 B == (A-l)
(A -1)
13N
Multiplying from
Multiplying the right
from the gives
by BBT gives
right by
-I T
BT))
B -1 (B 5 =
= BT (A-2)
(A -2)
T T -1
BBT is a square
BB matrix of
square matrix size (3N
of size -6) xx (3N
(3N-6) and will
-6) and
(3N-6) (BBT)) -l..
inverse (BB
will have an inverse Therefore
_ -i rn rp _ "1
B -1 = BT1 (B B ) -1
(B BT) (A-3)
(A -3)

To find (BT) we note

(BT )~-1 we definition that
by definition
note by that
(BT ) (BT) -1 = I3N
(BT) (A-4)
(A -4)
= I3N
Also if you take
if you the transpose
take the eqn.(A-l)
transpose ofof eqn.(A -1)
(BT)
(BT ) (B-1)T
(B" 1 ) 7 = I_3N (A-5)
(A -5)
I3N
-1 T it can
similar manner it
In aa similar be shown
can be that
shown that
of BB
Hence the transpose of inverse of
is the inverse B .
of BT. In
aa right B, "B^
of B,
right inverse of satisfying
Bi11 satisfying
-1 (A-8)
(A -6)
B BR = 13N _6
3N-6
exist.
does not exist. This is because BT
This is have an
B B is singular and does not have inverse.
an inverse.
Acknowledgements
The work
The work described above was done in
described above Prof. Warner L.
in collaboration with Prof. Peticolas. The
L. Peticolas.
author
author is very grateful
is very grateful to Prof. for his
Prof. Peticolas for kind help,
his kind guidance and
help, guidance introducing
for introducing
and for
the fascinating world of molecular vibrations and
to the
him to and resonance spectroscopy .
Raman spectroscopy.
resonance Raman II
Prof. Dennis
also wish to thank Prof.
also P. Strommen,
Dennis P. did the
who did
Strommen, who Uracil,
the calculations on Methyl Uracil,
all his
for all
for help and encouragement. Support
his help Chemistry, University
by the Department of Chemistry,
Support by of
University of
Oregon,
Oregon, and
and the
the School Optometry, University of
School of Optometry, Berkeley is
at Berkeley
California at
of California acknowledged.
is acknowledged.
References
1.
1. Blazej, D. C.
Blazej , D. and W.
C. and Peticolas, Proc.
L. Peticolas,
W. L. Proc. Natl.
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273 (1977).
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C. and P. Cross, Molecular
C. Cross, Vibrations, McGraw
Molecular Vibrations, Hill,
McGraw Hill,
(1955) .
New York (1955).

306 //SPIE
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 5.
5. Mclntosh,
McIntosh, D.D. F., and K.
F., and K. H.
H. Michaelian,
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C. Blazej,
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