Acta Ciencia Indica, Vol, 12 (P), No.

4, 80 (1986)

DEPENDENCE OF VIBRATIONAL CONSTANTS OF DIATOMIC OXIDES ON ELECTRONEGATIVITY AND VALENCE ELECTRONS Virendra Kumar Jain, A. K. Misra and Z. H. Zaidi
Department of Physics, Jamia Millia, Jamia Nagar, New Delhi-ll0025

"

:.'

J"

Received:'

August 29, 1986

A new empirical relation for calculating the vibrational frequencies of diatomic oxide molecule using known values of electronegativity and the number of valence electrons of constituent atoms is proposed. Validity of the relation is tested by comparing the calculated values with the experimental values for a number of diatomic oxides, Agreement between the two values is found to be good. Numerous attempts have been made to correlate different molecular cons.tants by empirical or semiempirical relations. The vibrational constant (we) is one such important molecular constant and several relations 11-8] have, been suggested for its calculation. Clark [5] suggested that any satisfactory relation for calculating we should contain u, the reduced mass of the molecule, His expectations were further supported by the observations made by Carrelli and Trautleur Purbrick [10] also found a similar dependence on reduced mass. His relation was of the form we=a+cub

we=(Aju)+B where A and B were constants . Hussain form we = qxlu

.CJ,

... (2) of the

... (3)

[12] proposed

a relation

for homonuclear diatomic molecules when and p were constants and x was the . "electronegativity of the atom. Goodfriend [13] used this relation (3) in the form

'

wedq(xA for heteroatoms, electronegativites Singh and relation as

XB) Ij2up

(4)

where XA and XB were the of the constituent atoms. Mathur [14] modified this

(1)

wherej-zr; b, and c were constants. This relation, however', indicates that we has linear relationship with reduced mass. Krasnov and Maksimov [11] suggested a relation of the form

we=q (XA XB)PjU Ij2

... (5)

All these relations indicate that we has inverse relationship with reduced mass. out Krasnov and Maksimov [II] pointed that the exact dependence of we on

Tyj612

Dependence of Vibrational

Constants

81

reduced mass, must take into account the type of chemical binding between the constituent atoms of the molecule. However, their relation does not appear to contain any molecular parameter which could be said to depend upon chemical binding. Now, considering the nature of Chemical binding and electronic configuration of the atoms, Pauling [15] defined electronegativity as the power of an atom in a molecule to attract electrons to itself. Walsh [16] found a correlation between the stretching force constant ke of hydrides and Pauling's electronegativity values. Wilmshurst [17] suggested that Pauling's electronegativity values were directly proportional to the square root of the stretching force constants of hydrides. This suggestion may be expressed as
xy(ke) ... (6)

ing in between the constituent atoms. Therefore, we should be a function of the prod uct of the electronegativities and the number of valence electrons of the constituent atoms. Symbolically
-we=fJ (xAnB,xBnA) ... (9)

where nA, ne are the number of valence electrons associated with atoms A and B respectively. We intend to call XAI1Bas the 'valence force' acting between atom and A and valence elecctrons ns- Thus, the dependence of we on reduced mass, electronegativity and the number of valence electrons could be expressed as
we=k (xAnB,xBnA) ... (to)

where k is a constant for each group subgroup of the periodic table.

or

Because of the fact that

ke=4n2uwe2c2 (7) (c being velocity of light).

the vibrational frequency of a hydride molecule should have a linear relationship with electronegativity. This deduction is obvious from the fact that during the vibration of a hydride molecule, displacement of the hydrogen atom would in turn cause a displacement of the valence electrons in the potential field of the heavier atom. In a vibratory link (A-B) both A and Bare displaced with respect to the centre of gravity of the bonding electron cloud. This led Gordy and Thomas [I8] to suggest that in a diatomic molecule we will be a function of the product of the electronegativities of the constituent atoms, i e.
we=f(xAxB) ... (8)

Discussion: In Table 1 we are reporting the results of calculations for distomic oxides using relation (to). These have been compared with the experimental values wherever available. The agreement is quite good in most of the cases. Values of we for some oxide molecules which have not been studied experimentally so far are predicted. Large deviations between the calculated and experimental values have been observed for MgO, BO, SnO, PbO, BiO, NiO and about ()% in case of BaO and PO. The observed value for NiO is reported to be uncertain [19]. Spectra for the molecule MgO, BaO, BO, PO, BiO and NiO have have not been studied in absorption [19] and if the observations are made only from studies in emission, one can not be completely sure whether the observed values values represent those of the ground state or not.

However, we feel that the valence electrons should also be taken into account while considering the nature of chemical bond-


82 ]
Acta Ciencia Indica

TABLE 1
Ccmparlson of Observed and Calculated we (in cm-1) Vibrational Constants

we

Group"

Molecule BeO MgO CaO . SrO BaO

Electronegativity 1.45 1.16

1.0

Calculated 1487.32 922.20 728.65 65606 630.98 1518.96 979.23 7535.) 703.09 67466 2169.82 I~EO 964.18 930.70 85052 188~.47 llGS.16 966.5 R23.77 758.60

Observed ) 487.32 785.0 733.4 653.2 669.8 1885.69 919.23 707.5 703.09

% Error
0 -17.5 +0.7 -04 +5.8 + 19.5 0 +1.8 0

IIA
(2) K=58.6336

o.ss
0.97 2.0 1.6 1.4 1.36 1.34 2.6 1.8

IlIA
(3) K=30.7846

BO

AIO
GaO InO TIO

IVA
(4) K=26.0144

CO SiO GeO SoO PbO

216982 12H.4 985.0 822.1 721.8 1904.12 1233.3 966.5 817 692.4

o
+0.7 +2.1 -13.2 -17.8

1.6
1.6 1.5 3.0 2.2 2.04 1.8 J.7 3.5 2.5 2.23 :?O

VA
(5) K=16.3816

NO PO AsO SbO BiO

+1
+5.5 0
-J

-9.6

VIA
(6) K-l1.9116

0,
SO SeO TeO PoO

1148.19 9l<i.02 795.43 777.84 1345.94 868 774.91 68404 565.76

1J4S.l9 915.43 79569

()

0 +0.3

z.o
4.0 2.9 U5 2.6 2.2

VIlA
(7) K=6.7454

FO CIO Bro
10

868 778.0 681.4

e +M
-0.4

AtO

Continued


Dependence of Vibrational Constants
IIIB (3) K=40.7451 IVB (4) K=31.9764 ScO YO LaO TiO ZrO HfO VO NbO TaO 1.3 1.22 1.2 1.3 1.33 1.4 1.5 1.6 1.7 1.5 1.6 2.0 1.6 1.9 2.2 1.7 1.8 20 1.7 2.1 2.1 1.7 2.0 2.2 1.8 1.4 1.4 971.55 850.57 813.34 1008.26 969.45 981.]5 997.30 1004.75 1028.69 898.8 904.18 ]092.48 839.5 945.49 1058.44 880.53 884.33 951.01 850 1000.82 969.03 714.20 797.65 851.09 658.56 490.4 475.52 851.09 665.0 [2]] 490.4 0 +1
0

(
971.55 852.5 811.6 1008.26 978.0 974.09 [:OJ 1011.56 989.0 1028.69 898.8 0 +0.2 -0.2 0 +0.8 -07 +1.4 -1.6 0 0

83

VB
(5) K=22.0924 VTB (6) K=16.6302 VIIB (7) K=12.5628 VIII (8) K=10.8734 VIII (9) K=9.3833 VIII (10) K=7.0828 IB
(11)

c-o
MoO WO MnO TcO ReO FeO RuO OsO CoO RhO IrO NiO

839.5

880.53 880.8

0 -0.4

850

615 [a]

-]6.2

reo
PtO CuO AgO AuO with in parentheses

K=4.6562 Numbers group. Collected J. Chern. Mulliken,

are the number of valence electrons and K is a constant for each

from Pritchard and Skinner, Chern. Revs., 55, 745 (1955) ; Gordy and Thomas, Phys., 24, 439 (1956) ; Allred and Rochow, J. Inorg., Nucl. Chern, 5, 264 (1958) ; J. Chim. Phys., 46, 497 (1949). Taken from American Institute of Physics Handbook, Third Edition, McGraw-Hill Book Company.

[a] Value is uncertain.

REFERENCES
ll] Morse, M., Phys. Rev., 34, 57 (1929). [2) Badger, R. M., J. Chern. Phys., 2, 128 (1934) [191

84
[3] Matuyama,

Acta Ciencia Indica

E., Nature Land., 133, 567 (1934).

[4] Clark, D., Phil. Mag., 18,459 (1944). [5] Clark, C. H. D., Trans. Faraday Soc., 33, 1398 (1937). [6] Fox, J. J. and Martin, A. E., J. Chem. Soc., 884 (1939).

P] Linnett,
l8]

J. W., Trans. Faraday Soc., 36, 1123 (1940). K. and Varshni, V. P., Indian J. Phys., 28, 209 (1954). P., Nuovocim., 14, 307 (1937).

Majumdar,

[9] Carrelli, A. and Trautleur,

[to]

Purbrick, H. L., Phys. Rev., 7J, 137 (1947).

[11] Krasnov, K. S. and Maksimov, A. I.. Cptika Spektrosk , 8. 403 (1960). 112] Hussain, Z., Can. J. Phys., 43, 1690 (1965). [l3] Goodfriend, P. L., Can. J. Phys, 45, 3425 (1967). [14] Singh, S. P. and Mathur, V. K., Indian J. Pure Appl. Phys., 6. 386 (1968). [15] Pauling, L., The Nature of the Chemical Bond, (Cornell University Press, Ithaca, New York), 58,75 (1939). [16] Walsh, A. D., Proc, R. Soc., 207A, 13 (1951). [17] Wilmshurst, J. K., J. Chern. Phys., 28, 733 (1958).

[18] Gordy, W. and Thomas, W. J. 0., J. Chem. Phys., 24, 439 (1956). [l9) Herzberg, G., Spectra of Diatomic Molecules, (D. Van Nostrand Company Inc.), (1950). Data, 1, (IFI/Plenum Data Company, LOS Angeles, California), to Diatomic

[20] Suchard, S. N., Spectroscopic (1975).

[21J Rosen, B., Ed., International Tables of Selected Constants, Molecules, (Pergaman Press, Oxford), (1970).

Spectroscopic Data Relative