JOURNAL OF blOLECULAR SPECTROSCOPY56, 484-493 (1975)

On the Rotational Contributions to the Dipole-Moment Derivatives

A. J. VAN STRATEN AND W. M. A. SMIT

Analytical CheGstry Laboratory, State University of Utrechl, Croesestraat 77A, Utrecht,

The Netherlands

In order to get dipole-moment derivatives, ae/&Sj, that are free from rotational contribu-
tions, we used Crawford’s method applied to a new type of reference molecule. The agreement
with earlier calculated rotational correction terms is good, the applicability of the new reference
molecule is wider. The rotational contributions to the a~/&$quantities are presented for a
number of C?,- and Csu-type molecules.

INTRODUCTION

It is useful to interpret the experimental infrared absorption intensities in terms of

dipole-moment derivatives with respect to the symmetry coordinates.
In the case of a molecule with a nonvanishing permanent moment, the motions repre-
sented by those symmetry species that include a molecular rotation produce @/X5~-
quantities containing a contribution from the rotation of the permanent dipole moment.
In comparing data on different isotopic species or on closely related compounds, the
only appropriate intensity parameters are those which are corrected for rotational
contributions.
This contribution arises from the condition that the angular and linear momentum
of the entire molecule is conserved in a perturbation of the equilibrium configuration
under vibration. This requires any alteration in the angular or linear momentum, result-
ing from a symmetry distortion, to be exactly compensated by an amount of rotation
or translation of the whole molecule with the same frequency. Since translational motions
do not affect the dipole moment of a molecule, only the rotational motions need be con-
sidered. As we know from pure rotational spectra, a molecular rotation contributes to
the absorption intensity if the molecule has a permanent moment.
In the derivation of the intensity sum rules Crawford (I) has given the mathematical
framework to calculate the difference in rotational contribution between two isotopic
molecules. Subsequently Dickson, Mills and Crawford (2) proposed a method to obtain
the absolute rotational correction for d~/&S’-quantities. However, the choice of the
rotational free reference molecule needed for such a calculation leads to difficulties in
some cases.
Here we present a new type of reference molecule, with a wider applicability.

THE ROTATIONAL CORRECTION

The experimental integrated intensity, Ai, of the ith fundamental absorption band is
related to the square of the dipole derivative, dy/aQ;, with respect to the ith normal

484

Copyright 0 1975 by Academic Press, Inc.

AU rights of reproduction
in any form reserved.
 ROTATIONAL CONTRIBUTIONS TO DIPOLE-MOMENT DERIVATIVES 485

coordinate, Qi, by
A i = (Norgi/3c2) (ap/aQi)” (1)
in the harmonic-oscillator-linear-dipole approximation (3). In Eq. (1) IV0 is Avogadro’s
number, c the speed of light, p the molecular dipole-moment vector, and gi the degree
of degeneracy of the ith fundamental.
The normal coordinates are defined in terms of a set of internal coordinates, R,
through the L-matrix: R = LQ (4). Thus we can write

5ELj$
aQi j I
or in matrix notation,
(w'aQ)= h%/W, (2)
e being the transposed L-matrix.
In the interpretation of intensity data one usually determines the dipole-moment
derivatives with respect to symmetry coordinates (5), which are taken as linear com-
binations of the internal coordinates, S = UR, leading to
(av/aQ) = tti(atr/aS). (3)
Our aim is to separate the contribution originating from the compensating rotation
accompanying a vibration from the dipole-moment derivatives, obtained from Eq.
(2) or (3). This requires the availability of a reference molecule in which vibration
produces no compensating rotatory motion. The definition of such a reference molecule
is given in the following section.
The dipole-moment derivatives obtained from Eq. (3) will be denoted by (ap/aS)~,
where the subscript A refers to the actual molecule under consideration. The theoretical
quantity needed will be denoted by (ap/aS)~, where the subscript R stands for the
reference molecule. The difference between these two parameters is the rotational cor-
rection, or in formula:
(a&S), = (a&S>‘4 - VAR. (4)
The columnvector, VAn, can be evaluated with the help of two additional coordinate
sets :
X: the vector of the 3N Cartesian displacement coordinates (N is the number of
atoms in the molecule).
e: the external coordinates (the six translations and rotations). The transformation
matrices between e, R, S, and X are defined as follows.
R = BX, B = (aR/aX), A* = (aX/aR)*,
S = UBX, UB = (as/ax), A*0 = (ax/as)*, (5)
@* = 0*x, 9* = (ae*/aX), (y* = (ax/a@*).
The matrices and vectors marked with an asterisk are isotope-dependent. The properties
of these transformation matrices for a given isotope are :
BE*= 0, @*A* = 0, BM*-‘jj = G*
BA* = Em+ @*a* = Ea, @*M*-‘g* = & (6)
A*B + a*@* = Em, g#M*& = N*-1
I
 486 VAN STKATEN AND SMIT

where G is Wilson’s kinetic-energy matrix (J), M is the diagonal matrix of the atomic
masses, and N is a 6 X 6 diagonal matrix containing the reciprocals of both the molecular
mass and the principal moments of inertia.
Crawford (1) derived a relation between the A-matrices of two different isotopes. For
the A-matrix of the reference molecule this relation reads

AR = AA - QT&AA, (7)
where the subscripts have the meaning as defined above.
From Eq. (7) one easily obtains

ub,(a,/ax) = uL(a~/ax) - uK4&&&L/ax), (8)

which is equivalent to Eq. (4). So the column vector of the rotational corrections can be
written as
VAR = {u~,gR){(YR(a~/ax)}. (9)
Since translational motions do not change p, we may rewrite the second part of VAR (I),
giving
0

(LR-
i3X
=
0

(wJyk- (di
I 7 (10)

(dri - h&k
oL0Lj - (p3,i i
where (~0)~ denotes the x-component of the permanent dipole moment and i, j, and k
are the Cartesian unit direction vectors. In the case of symmetry this column vector

FIG. 1. Definition of internal coordinates in (a) bent XIY molecules, (b) X&Y molecules, (c) pyramidal
XIY molecules, (d) X&Y molecules. Definition of dipole-moment direction and Cartesian coordinate
axes.
 ROTATIONAL CONTRIBUTIONS TO DIPOLE-MOMENT DERIVATIVES 4x7

Table I. Rotational c”rrections and symmetry coordinates in methyl

a
halides.

S4x= 6-i(2Lr,-Lr2-?‘r3)

-!
= 6 ‘(ZL-r,-h 12-Aii.~)
s5x

= 6 ~(2~,i,,-lli7-A,:3)
‘6x

X3CY p0 (D) Keference molecule Reference molecule

with mX = 0 with mC,mY x 1000

“4x “5x “6x “4x “5x “6x

H3CF -1.81 +0.!1798 +0.0894 -0.2085 +0.0797 +0.0892 -0.2082

D3CF -1.81 +o.l123 +0.1312 -0.3220 +0.1120 +0.1310 -0.3214

H3CCl -1.87 to.071 I +0.1)685 -0.1310 +0.0710 +0.0684 -0.1308

D3CC1 -1.87 +o. 1073 +0.1052 -0.2073 +u.1071 +Cl.lOSO -0.2069

113Cfk -1.80 t0.0651 +0.0586 -11.1003 +0.0650 +‘J.O586 -IJ.l002

I13CBr -I .su +o. 1009 +0.0914 -0.1587 +0.!007 +0.0913 -0.1584

H3CI -1.62 +rl.o542 +0.0471 -0.0755 +0.0541 +0.0471 -0.b754

D3CI -1.62 +0.0850 +0.0742 -0.1199 +0.0849 +0.0740 -0.1197

Leometrical parameters are the same as in Ref. 12.

often reduces to a very simple form, e.g., in the case of C’S, or Can symmetry there is
only a nonzero component of the permanent moment along the main axis of symmetry.
The UAAfiR term gives the translation and rotation set up in the reference molecule,
when its atoms execute the displacements appropriate to a symmetry distortion S in
the actual molecule. The AA-matrix can be calculated from (I)

(11)
The @z-matrix can be written easily.
Thus, after defining an appropriate reference molecule the calculation of the rota-
t ional contributions is straightforward.

THE REFERENCE MOLECULE

The determination of the rotational corrections is only possible if we can define a

reference molecule (a hypothetical molecule, being an isotope of the original one),
which possesses rotation-free internal coordinates.
488 VAN STRATEN AND SMIT

Table II. Definition of symmetry coordinates and rotation%1 contribu-

tions in Br3CH/D.a

= 6-‘(2A,S,-.AE,-AK3)
s4x

= 6 -1 (2ArI-k-Ar3)
s5x

= 6-l (2Aal-Aa2-A~3)
‘6x

Reference molecule Reference molecule with

v. i!;) with mBr=O x 100 000

“C~mli/D

v4x V5x ‘6x V4x V5x “6x

Br3CH to.99 +o.e049 +0.1251 -0.0104 +0.8011 +0.1251 -0.0097

Br3CD. +0.99 +0.?3014 +0.1229 -0.0123 +0.7994 +0.1229 -0.0119

a
Geometrical parameters from Ref. 13.

The only rotation-free molecule known in the literature is a molecule in which isotopes
of zero mass are introduced for atoms which are not situated on the main molecular
symmetry axis. For example, in the case of XEY-molecules (2,6), where X, Y = H, D,
F, Cl, Br, and I, one has used as a reference molecule the isotopic molecule containing
zero X-masses. During all vibrations of such a reference molecule the CY-bond will
maintain a fixed direction and thus there is no compensating rotational motion. Also

Table III. Bent triatomic molecules X2!f.

a(? Ref. Uo(D)

XzY

I--
H2O 0.9584 104.45 14 -I .85 -0.0771

DP 0.9584 104.45 14 -I .R5 -0.1436

v 1.34 92.33 15 -0.97 -0.n15li

D2S 1.34 92.33 15 -0.97 -u.o302

: 02s 1.433 119.33 15 +I .47 +0.1810

I
 ROTATIONAL CONTRIBUTIONS TO DIPOLE-MOMENT DERIVATIVES 489

Table IV. Definition of symmetry coordinates and rotational contributions

in X2CY-molecules.

S4
= 2-1(Ar1-hr2)
I
2
Sj = 2 (‘w,-sIJ,)

= h” (out-of-plane)
‘6

H2C0 1.09 1.213 120 16 -2.33 +0.11aa -0.3419 -0.2279

JJ2CO I .09 I.213 120 16 -2.33 +0.1619 -0.5152 -0.3575

F2CO 1.312 1.174 108.0 17 -0.95 -0.0385 -0.4750 -0.3959

C12C0 1.746 I.166 III.3 7 -1.18 -0.1244 -0.7109 -0.6010

HK2CO 2.05 1.13 I IO 7 -1.38 -0.2166 -0.9010 -0.7967

F2CS 1.312 1.56 108.0 IO -0.05 +0.0020 -0.0186 -0.0157

C12CS 1.746 1.56 III.3 IO -0.28 -0.0079 -0.1400 -O.llll

in the case of X&Y (7-11) molecules (X = H, D, F, Cl, Br; Y = 0, S) the introduction

of an X-isotope of zero mass provides a usable reference molecule.
However, this procedure cannot be followed in bent XZY- or pyramidal XsY-mole-
cules. Introduction of an X-isotope with zero mass in such molecules leads to indefinite
elements of the @R-matrix, thus prohibiting the calculation of the rotational corrections
(see Eq. (9)).
In order to overcome these difficulties, we propose the following reference molecule.
Replace the atoms of the actual molecule which are situated on the main symmetry axis
by isotopes that are a factor of a thousand or more heavier than the original atoms.’
In such a reference molecule, the compensating rotational motions are negligable, be-
cause of the large masses of the substituted isotopes. This is also valid in the case of
X2Y- and XsY-molecules, while no difficulties arise in the calculation of the elements of
l3~. In the case of X&Y-molecules (see Fig. Id) with X = H or D and Y a halogen
atom, a multiplication factor of 1000 for the C and Y atom is very satisfactory, due to
the low X-masses. It can be seen from Table I that the use of this reference molecule
leads to results which agree within 1% with those obtained using a reference molecule
with zero X-masses.
If the X-atom has a large mass e.g., BraCH, the multiplication factor must be 10 000
or even more (see Fig. 2 and Table II).
1If three or more atoms are situated on the main symmetry axis, only two adjacent nonterminal atoms
must be replaced by heavy isotopes (e.g., the two C atoms in methylcyanide).
19c VAN STRATEN AND SMIT

FIG. 2. Rotational correction terms I’<, for Br&H/D as a function of the factor by which the atoms
on the main symmetry axis (C and H/D) were multiplicated. Sdr, Sbz,and .SBzare symmetry coordinates
as defined in Table 11.

REMARKS ON THE CALCULATION OF ROTATIONAL CONTRIBUTIONS

In order to ensure that the rotational correction terms can be interpreted unam-
biguously, it will be necessary that clear definitions are used with respect to:
1. The dipole-moment direction. The dipole-moment vector is directed from the center
of the negative charges to the center of the positive charges. (a&as) and ‘Vg-values
are positive when positive charge is displaced in the positive [-direction (E = x, y, or z).
2. The Cartesian coordkate azes. The Cartesian coordinate axes are defined so as to
form a right-hand coordinate system (see Fig. 1) i X j = k, and so on, cyclically.
3. The direction of rot&ion. A rotation about the t-axis is defined as positive when its
rotation-vector WCpoints along the positive .&asis. As a consequence the general form
of the @-matrix elements can be given as follows.

~1 (T,) : Pl,3i-2 = mi/mtot, P1,3d-1 = 0, PL3i = 0,

PZ(T~): P2,3i-2 = 0, P2.3i-1 = mi/fht, p2,3i = 0,

p3(Tz) : P3,3i--2 = 0, P3,3i-1 = 0, P3.3i = mil%d,

P4(Rz) : P4,3i--2 = 0, P4,3i-1 = -%%i/I+~, P4,3i = miyoi/Izz,

PS(&) : P5,3i-z = mizoi/l,,, P5,3i-1 = 0, P5,3i = - %.Voi/I,,,

PG(&) : P6,3i-z = -miyoi/Ixz, P6,3i--1 = ~Joil~2r, P6,3i = 0,

where i = 1, 2, . . ., N

&i = the equilibrium 6 distance of atom i to the center of mass (E = x, y, z).

I,,, I,,, I,, are the principal moments of inertia.
 ROTATIONAL CONTRIBUTIONS TO DIPOLE-MOMENT DERIVATIVES 491

3. The symm.etry coordinuies. The symmetry coordinates are built up from internal
coordinates (e.g., a7i, Aa,). The internal coordinates are taken as increments in bond-
length and interbondangles. If scaled symmetry coordinates are used, the scaling factors
must be clearly indicated. The scaling factors influence some of the U-matrix elements
and consequently the rotational correction terms (see Eq. (9)).

Table V. Pyramidal X3Y molecules.

S 6-’ (2Ar I-Ar2-.Ar3)

3x =

6-+2Aal-Aa2-Au3)
s4x = rxI

Reference molecule (“y x 1000)

r,(g) a(‘) pa(D) Ref. _
x3y
V3x(D/% V4x(D/a)

H3N 1.014 106.78 -1.47 15 -0.0670 -0.0375

D3N 1.014 106.78 -1.47 15 -0.1174 -0.0657

F3N i.371 102.15 +0.235 15 +0.0500 +0.0273

H3P I .419 93.5 $I,& I5 -0.0103 -0.0053

D3P 1.419 93.5 -0.55 15 -0.0196 -0.0101

F3P 1.563 96.9 +1.03 18 +O. 1635 +0.0864

C13P 2.043 100.10 +O*78 15 +0.1120 +0.0604

H3As I .523 92 -0.22 15 -0.0016 -0.0008

D3As 1.523 92 -0.22 15 -0.0032 -0.0016

F3As 1.712 100 +2.59 15 +0.2136 +0.1152

C13As 2.161 98.42 +I.59 15 +O. 1548 +0.0826

H3Sb 1.7 12 91.5 -0.12 15 -0.0005 -0.0003

D3Sb 1.712 91.5 -0.12 15 -0.0010 -0.0005

C13Sb 2.325 99.5 +3.00 15 +O. 2004 +o. 1077

492 VAN STRATEN AND SMIT

Table VI. xp molec"les.a

Symmetry coordinates as in Table II

ac?
I Rotational corrections
I

tT--T-+
X3CY rcx (2% r,,(X) PO(D) Reference molecule (mC,my x 100 000

1 I I

aGeometrical parameters as in Ref. 19.

I 1

CALCULATIONS AND CONCLUDING REMARKS

Using the reference molecule as proposed here, rotational contributions were calcu-
lated for the following types of molecules. Bent XZY molecules: Czu (see Table III and
Fig. la) ; X&Y molecules: Czu (see Table IV and Fig. lb) ; pyramidal XsY molecules :
Csu (see Table V and Fig. lc); and X&Y molecules: Cl” (see Table VI and Fig. Id).
It is evident from Table I that the results obtained with our reference molecule are the
same as those obtained with Crawford’s reference molecule. The reference molecule as
proposed here leads to correct rotational contributions for all small molecules, with the
exception perhaps of triatomic linear ones and molecules in which no n-fold axis (n 3 2)
is present. In the case of those molecules difficulties arise, by applying a Crawford’s
type reference molecule as well as our type of reference molecule. The choice of a rota-
tional free molecule is not quite clear in such cases, which leads to some arbitrariness
in the absolute rotational contribution.
However, if the molecular symmetry is C, or Iower a sensible choice can sometimes
be made (e.g., the C and 0 atoms in methanol, the C-O bond being almost a 3-fold
axis). In “large” molecules (eight or more atoms) the rotational contributions can be
ignored.

ACKNOWLEDGMENT

Our thanks are due to Dr. B. L. Crawford, Jr., for reading the manuscript prior to publication.

RECEIVED: October 30, 1974

REFERENCES

1. B. CRAWFORD, JR.,J. C/rem. Pltys. 20, 977 (1952).

2. A. D. DPXSON, I. M. MILLS, AND B. CRAWFORD,JR., J. Cltetn. Phys. 27, 445 (19.57).
3. B. CRAWFORD, JR.,J. Chn. Phys. 29, 1042 (1958).
 ROTATIONAL CONTRIBUTIONS TO DIPOLE-MOMENT DERIVATIVES 493

4. E. B. WILSON, JR., J. C. DECIUS, AND P. C. CROSS, “Molecular Vibrations,” McGraw-Hill, New

York, 1955.
5. J. OVEREND, “Infrared Spectroscopy and Molecular Structure” (M. Davies, Ed.), Chap. X, Elsevier,
New York, 1963.
6. J. W. RUSSELL, C. D. NEEDHAM,AND J. OVEREND,J. Chem. Phys. 45,3383 (1966).
7. M. J. HOPPER, J. W. RUSSELL,ANDJ. OVEREND,J. Chem. Phys. 48, 3765 (1968).
8. D. C. MCKEAN, R. E. BRUNS, W. B. PERSON,AND G. A. SEGAL,J. Chern. Phys. 55, 2890 (1971).
9. 1~. E. BRUNS ANDR. K. NAIR, J. Chew Phys. 58, 1849 (1973).
10. M. J. HOPPER, J. W. RUSSELL,ANDJ. OVEREND,Spectrochim. Ada 28A, 1215 (1972).
Il. R. E. BRUNS ANDW. B. PERSON,J. Chew Phys. 58,258s (1973).
12. J. A~nous AND I. M. MILLS, S#&xhinz. Ada 19, 1567 (1963).
13. S. KOJ~MA,K. TSUKADA,S. HAGIWARA,M. MITUSHIMA,ANDT. ITO, J. Chem. Phys. 20,804 (1952).
14. “Interatomic Distances” (L. E. Sutton, Ed.), Special Publication no. 11, The Chemicai Society,
London, 1958.
15. W. GORDY, W. V. SMITH,AND R. F. TRAMBARULO,“Microwave Spectroscopy,” Wiley, New York,
19.53.
16. K. TAKAGI ANDT. OKA, J. Phys. SOC.Jupm 18, 1174 (1963).
17. V. W. LAURIE, D. T. PENCE, AND R. H. JACKSON,J. Chest. Phys. 37, 2995 (1962).
18. E. HIROTA ANDY. MORINO, J. Mol. Spectrosc. 33,460 (1970).
19. S. N. GHOSH,R. TRAMBARULO,ANDW. GORDY,J. Chem. Phys., 20, 605 (1952).