New Form of Molecular Potential Function for Use in Molecular Vibrational Analysis

Emil J. Slowinski Citation: J. Chem. Phys. 23, 1933 (1955); doi: 10.1063/1.1740608 View online: http://dx.doi.org/10.1063/1.1740608 View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v23/i10 Published by the American Institute of Physics.

Additional information on J. Chem. Phys.

Journal Homepage: http://jcp.aip.org/ Journal Information: http://jcp.aip.org/about/about_the_journal Top downloads: http://jcp.aip.org/features/most_downloaded Information for Authors: http://jcp.aip.org/authors

Downloaded 12 Apr 2012 to 133.41.91.47. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions

THE

JOURNAL

OF

CHEMICAL

PHYSICS

VOLUME

23,

NUMBER

10

OCTOBER,

1955

New Form of Molecular Potential Function for Use in Molecular Vibrational Analysis
EMIL

J.

SLOWINSKI, JR.

University of Connecticut, Storrs, Connecticut

(Received August 10, 1953) A molecular potential function which takes simple and direct account of intramolecular strains is proposed. The parameters in the function are the conventional bond-stretching and angle-bending force constants and the strain-free magnitudes of the bond lengths and bond angles. The function is applied to the analysis of the vibrations of XY2 molecules with C2V symmetry. Calculations based on the zero-order frequencies of H 2 0 and D 20 indicate that a three-parameter function is adequate for these molecules. All molecules studied with the function show a moderate attraction between the end atoms of the molecules, resulting in a decrease in the size of the bond angle from the strain-free value. For compounds of the oxygen family with hydrogen the bond angle at zero strain appears to have a constant value equal to 120.

C LASSICAL mechanics offers several methods for the analysis of the vibrations of linearly-coupled
systems. These methods involve the expression of the potential and kinetic energies of the system in terms of suitable coordinates. Given a system (see Fig. 1) consisting of several masses connected by conventional springs, one can immediately express the potential energy:

where the first sum is taken over springs between masses, and the second over springs in the angles. kil is the force constant of the spring between the ith and lth masses, Lil is the instantaneous distance between them, and Ailo is the distance in the event that there is no strain in the spring. Similarly, k j is the force constant of the spring in the jth angle, Aj is its instantaneous magnitude, and Cijo its magnitude when there is no strain in the spring. The form of the function is obvious, given the system. It allows for all possible strains within the system at equilibrium, and, indeed, one would not consider expressing the potential energy in the classical problem in any other way. The methods used in present-day problems in molecular vibrational analysis are essentially classical; atoms are considered to be mass points in a linearly-coupled force field and are assumed to move only infinitesimally from their equilibrium positions. This approach has been shown to be consistent with results as obtained from direct use of quantum-mechanical reasoning, and is almost universally employed. However, the potential functions which have been assumed for molecules are not of the form (1), which we would like to propose as being a reasonable function, but rather (in the simplest case) are of the following type:
(2)

rather than finite changes from the strain-free configuration. Basically, function (2) assumes what function (1) does not; namely, that at equilibrium, there is no potential energy in the molecule and hence no intramolecular strain. Therefore, even if the molecular force field were of the simple form shown in Fig. 1, function (2) would not be directly applicable to the vibrational analysis problem, except in the special situation where the molecule existed at equilibrium under no strain. To improve correlation between calculated and observed vibrational frequencies function (2) has been modified in various ways. One of the most successful has been a function of the type suggested by Urey and Bradley, l which takes essentially the following form:

V =tL:k il 6.L i ?+ L:k;z'6.L il +tL:k j 6.Al+ L:k/6.A j (3)

In this function the terms have the same meaning as before, and kJ and k/ have the appropriate dimensions. One finds on investigating the k' terms that they depend on intramolecular strains in the equilibrium configuration. In this sense one can say that functions (1) and (3) are similar. Where function (1) introduces the strain terms into the sums involving the fundamental force constants, function (3) adds terms taking account of strain to the previously-existing ones. On comparing the two functions it seems reasonable to suggest that those of form (1) have some advantages not possessed by those of the Urey-Bradley type. The parameters in the proposed function have a direct and easily-visualized significance, being either conventional force constants or strain-free magnitudes of bond lengths

where the sums are taken in the same way as in (1), FIG. 1. A simple linearly-coupled system. but 6.L il and 6.A j are infinitesimal changes in bond length and angle from the equilibrium configuration, 1 H. C. Urey and C. A. Bradley, Phys. Rev. 38, 1969 (1931). 1933

Downloaded 12 Apr 2012 to 133.41.91.47. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions

1934

EMIL J. SLOWINSKI, JR.

and angles. The (k')'s have no such simple meaning. Simanouti,2 in a treatment of a group of molecules with a Urey-Bradley field, never reports some of the k' values at all, but rather goes directly to the intramolecular forces. Also, the proposed function (1) attributes, in the first instance at least, intramolecular strain to the inability of the bond lengths and angles in the molecule to fit easily together, where the UreyBradley field introduces strain terms in a more formal way. Generalizing, one might say that the proposed function makes a more literal interpretation of the familiar model for the molecule than does the UreyBradley field. Application of the proposed function to problems of molecular vibrations yields some interesting results. The approach for XY 2 molecules of the H 20 type, shown in Fig. 1, will be outlined. The Lagrangian method is used with Cartesian displacement coordinates. The potential energy of the XY 2 molecule is taken to be, according to (1):

For the XY2 molecule Eq. (4) takes the form:

X(OLI3_ OLI3] )]+ksI:.AsOAs oqu oqu equit. oqu OAs )] . +k.[ (Aso-aso) ( - -OAs] oqu oqu equit.

Applying the Lagrangian equations to the system, and noting that at equilibrium a balance of forces exists within the molecule, we obtain for the generating equation for the secular determinants (general form) :
oLi! w2 ul:.qu= 'Lki!I:.Li!-m oqu OL' I OL'I] ) + 'Lkil(Lilo-Ailo) ( --' - - - ' . oqu oqu equit.

The I:.L's, I:.A s, and the various associated derivatives are fairly easily expressed in terms of the Cartesian displacement coordinates by means of well-known or readily-derived formulas and the secular determinants thereby formed. For the totally-symmetric class the resulting frequency equations are:
(WI2+W22)my=kxy[1+2my D2 mx y 2m + ( 1+--G2) ( 1 - mx L 120

AI20)] +2k yy

2 WI 2W 2. - - - mx+2my
(4)

k [1- A120]
Xy2

L 120 ks 2kxyk s - - [ A so -a so J2+-L1204 L1202

2

where mu is the mass of the uth atom, I:.qu is one of its Cartesian displacement coordinates, L ilo and A jo are magnitudes of bond lengths and angles at equilibrium, derivatives are taken in the instantaneous or, as noted, in the equilibrium configuration, and all other terms are as previously defined. From this equation it is apparent that the inclusion of possible strain has simply introduced extra terms into the force Eq. (4), and that in the absence of strain the equation reduces immediately, as expected, to the one obtained by application of the Lagrangian to function (2).
~

4k yy k. +--[C2+CD(A so -a so )]. L1202

For the B2 class the equation is

2my 2my wimy=kxy [ 1+--D+ ( 1+--D2 ) ( 1 - mx mx L 120

A120) ]

1'. Sirnanouti, J. Chern. Phys. 17, 848 (1949).

4k. my --GD(A. o-a so )-+2k yy 1 - - , L1202 mx L 130

(A130)

Downloaded 12 Apr 2012 to 133.41.91.47. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions

NEW FORM

OF

MOLECULAR

POTENTIAL FUNCTION

1935

where C=sin(A /2); D=cos(A.o/2); A12O=A230; L 120

=L 230

TABLE

II. Vibrational parameters of XY2 molecules determined from fundamental frequencies.

k.
PI

From the condition that a balance of forces must exist at equilibrium we obtain:

Molecule

hUO

P2

va

A,o o

kxy

--1
U80 0

L1202

Ll20

and

A120) k xy ( 1 - - +2k yyC2 (A130) =0. 1-L 120 L 130

This system is one with three conditions on four independent parameters. To solve for the parameters one needs to use the frequencies of isotopic pairs. One such pair of molecules is represented by H 20 and D 20, where there is the added advantage that the zero-order frequencies are known. These frequencies were used to determine the parameters for the water molecule, with one notable result. The value of k yy , the force constant for the distance between nonbonded atoms was found
TABLE

H 2O D 20 H 2Se D 2Se F 20 ChO S0 2

3652 2666 2260 1630 830 680 1151

1595 1179 1074 745 490 330 519 em-1

3756 2789 2350 1696 1110 973 1361

105 105 90 90 104 111 120

7.5823 7.7075 2.9716 3.0412 4.7565 4.4255 9.8886

0.8544 0.8986 0.4852 0.4651 1.4262 1.0241 0.9442

120.5 122.7 121.3 122.7 145.9 150.8 129.9

0.0397 0.0470 0.0893 0.0874 0.2805 0.2337 0.0285

XI0 6 dynes/em
'--------..----'

a Vibrational frequencies are taken from G. Herzberg I nfrared and Raman Spectra (D. Van Nostrand Company, Inc., New York, 1945).

1. Vibrational parameters for H 20 - D 20 isotopic pair, determined from zero-order frequencies.

k.
PI P2 P3

A.!oO

kxy

Lao 2

aBo o

H 2O 3825.32 1653.91 3935.59 10427' 8.317 0.931 121.0 D 20 2758.06 1210.25 2883.79 10427' 8.293 0.956 122.6 D 20 2763.3 1208.0 2883.6 (calc) em-1 X 105 dynes/em
'-----v----'
a Vibrational frequencies are those reported by Darling and Dennison, Phys. Rev. 57, 128 (1940).

to have a value of about 0.09X 105 dynes per cm' which is only about one percent of the 0- H bondstretching force constant. In the equations in which they appear the contributions of terms in k yy is also small, being about 1.5% in one case and about 5% in the other. The value of k yy is very sensitive to the vibrational frequencies which are used, and a change of one or two wave numbers in a single frequency is sufficient to change its size by a factor of two. This very small calculated size and effect of k yy has led to the postulate that in these molecules this force constant may reasonably be taken to be zero, though the force between the end atoms is not zero. This assumption, suggested by the results with the water molecule, has been extended to other XY2 molecules. Since that

assumption reduces the number of independent parameters by one, it becomes possible to calculate the vibrational parameters for a molecule in terms of its vibrational frequencies, with no need for the use of isotopic pairs. The results of such calculations are given in Tables I and II. In Table I, the parameters for H 20 and D 20 have been independently determined on the basis of the three-parameter function and the zero-order frequencies of the molecules. In the last line of the table the parameters of H 20 as obtained above have been used to calculate the zero-order frequencies of D 20. The mean deviation from the reported frequencies is 0.13%. In Table II, the parameters for several molecules are given on the basis of the fundamental frequencies and the three-parameter function. It is to be noted that in all cases studied, the bond angle in the molecule at equilibrium is found to be smaller than the angle would be in its strain-free state, indicating a moderate attraction exists between the nonbonded atoms in these molecules. In all calculations involving water and hydrogen selenide the strain-free bond angle Ci so appears to have the same value, about 120, although the angle magnitudes at equilibrium are known to differ by 15. Decrease in bond length due to the attraction between end atoms varies from about 4% for water to about 28% for F 20. The approach to molecular properties through the proposed potential energy function shows, we believe, some promise, and at present work is progressing on the application of the function to the vibrations of NH 3and CH4-type molecules.

Downloaded 12 Apr 2012 to 133.41.91.47. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions