Electric Dipole Moment of SiO and GeO

John W. Raymonda, John S. Muenter, and William A. Klemperer

Citation: The Journal of Chemical Physics 52, 3458 (1970); doi: 10.1063/1.1673510
View online: http://dx.doi.org/10.1063/1.1673510
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 52, NUMBER 7 1 APRIL 1970

Electric Dipole Moment of SiO and GeO*

JOHN W. RAYMONDA, JOHN S. MUENTER, AND WILLIAM A. KLEMPERER

Department of Chemistry, Harvard University, Cambridge, Massachusetts 02138

(Received 25 September 1968)

The molecular beam electric resonance spectra of SiO and GeO have been measured. The electric dipole
moments (in Debye) of SiO and GeO in the lower vibrational states are:
V 28SiO 74GeO
0 3.0982 3.2824
1 3.1178 3.3032
2 3.1372 3.3239
3 3.1574
The difference between observed and calculated dipole moment is quite similar in CO and SiO.

INTRODUCTION while GeO was produced by the reaction

The electric dipole moment of carbon monoxide has Ge(l) +Ge02(s)~2GeO(g).
been of continual interest in structural chemistry. That
the moment is almost zero, 0.1 D,1 is surprising. Self- SiO production was carried out in a resistively heated
consistent field calculations2.3 give a moment of 0.2 to tantalum oven fitted with an inert refractory liner of
0.3 D, thus quantitatively explaining a moment of this boron nitride,S which was necessary because molten
magnitude. The sign of the calculated moment is, how- silicon is apparently very reactive toward all metals.
ever, almost certainly opposite to that found in nature. 4 The temperature ranged from 1500 to 1950°C during
While a discrepancy of 0.3-0.4 D in the calculation of the experiment. The intensity of the SiO beam was
an electric dipole moment should not be particularly monitored by m/e=44 (SiO+).
disturbing, the sign reversal is qualitatively dramatic GeO was produced directly in the tantalum oven at
and has therefore attracted much attention. temperatures between 800 and 1100°e. Molecules con-
The present measurement of the electric dipole mo- taining all the spinless Ge isotopes were observed. The
ment of SiO and GeO provides data for a set of mole- GeO beam was monitored by observing the fragment
cules closely related to CO. Since McLean and Yoshi- ions Ge+, m/e= 70, 72, 74 and 76, which were more in-
mine3 have recently produced SCF calculations for tense than corresponding GeO+ signals.
SiO of a quality comparable to those available for CO,
the present measurements permit a test of the quality RESULTS
of the SiO calculations. SiO and GeO have II: ground states and the isotopic
With this amount of experimental and theoretical species studied in this work have spinless nuclei; thus,
information about CO and SiO available, a detailed the observed spectra were without hyperfine structure.
comparison of the dipole moment of these molecules is For the lower vibrational states of SiO, the transition
made. Included in this paper is a measurement of the studied was J= 1, I AMJ I = 1. For GeO, the transitions
electric dipole moment of GeO. To our knowledge, J= 1, I AMJ I = 1 and J= 2, I AMJ 1= 1 were studied.
SCF calculations do not exist for GeO; therefore, dis- Table I lists the species studied, their vibrational states,
CUSSIon of GeO is limited to empirical contrast with the electric field and observed transition frequencies for
SiO. the J = 1 transitions, and the dipole moments calcu-
EXPERIMENTAL lated from these data. These calculations include
fourth-order Stark corrections but neglect any contribu-
The molecular beam electric resonance spectrometer> tion from molecular polarizability. The rotational con-
is a fiopout system with quadrupole A and B fields. stants used are those of Torring. 9 •lo We were not aware
The universal detector is a Weiss-type electron bom- of Torring's recent study of SiO during the course of
bardment ion source6 followed by 60°-sector magnetic this work and we have remeasured the 28SiO J = 0 to
mass analyzer. The production of molecular beams J = 1 rotational transition for the ground vibrational
stable in intensity for several hours was the only diffi- state, obtaining 43423.85 MHz, in excellent agree-
culty in the present work. Both molecules were formed ment with Torring.
in the source oven by high-temperature reactions. The electric dipole moment is observed as a function
SiO was produced by the reaction7 of vibrational energy. The data may be fitted to a power
series in (v+t). Retaining the linear term only, which
3458

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 ELECTRIC DIPOLE MOMENT OF SiO AND GeO 3459

fits the observed data to 0.001 D, TABLE II. Comparison of observed and calculated dipole moments
and dipole derivatives.
J.L.= J.L.+J.L I (v+t) ,
for SiO lLe(D) alL/ar I reD/ A
J.L.= 3.0882 J.LI = 0.0197,
Obs Calc Obs Calc
and for GeO
J.L.= 3.2720 J.LI = 0.0208.
CO -0.105 0.280 3.0 5.03
J.L. is interpreted as the vibrational average of J.L(r). SiO 3.0882 3.677 2.22 5.06
The relationship between the distance derivatives of GeO 3.2720
J.L(r) and J.LI has been given many times,!!
(V+t)J.LI = (r-re)v(dJ.L/dr) Ire+t Historically J.Le and dJ.L/ dr have been the principally
X «( r- r.) 2)v (d2J.L!dr2) ITO, discussed dipole data. In order to obtain dJ.L/ dr from
J.LI, some estimate of d2J.L/ dr 2 is required. Two estimates
(r-r e).= (a.re/2Be+3Bere/We) (v+t) , are possible. The first is to use the computed value of
«(r-r.)2).= (r.2B./w.) (v+t). 1.5 D/12 • The second is to assume a simple two-param-
eter function for J.L(r) that is qualitatively correct.
Using the microwave spectroscopic values9 •10 for r., (3e, This function should be zero at r= 00 and should ap-
and a., and optical spectra values!2.13 for We, J.LI may be proach zero as the third power of r as r approaches the
evaluated as united-atom limit. 14 If we assume J.L(r) = Ar exp[ -ar],
then
SiO:
2
J.LI = 7.89X 10-3 (dJ.L/dr) + 1.33X 10-3 (d2J.L/dr2) , d J.L = [(dJ.L)2 / J.L] _ 3J.L •
dr2 dr r2
GeO:
For SiO, this gives d2J.L/dr2= -1.3 D/12.
J.LI = 7.55X 10-3 (dJ.L/dr) + 1.30 X 10-3 (d 2J.L/dr2) • Both of these estimates give a small value for d2J.L/ dr2,
Preempting our discussion of these results, for SiO but of opposite sign. We shall therefore assume that
McLean and Yoshimine calculate d2J.L/ dr2 = 0 for both SiO and GeO for purposes of ob-
taining dJ.L/dr from J.LI. This gives for SiO
dJ.L/ dr= 5.06 D / 1
and dJ.L/dr= 2.5±0.5 D/1
d2J.L/dr2= 1.5 D/12, and for GeO
dJ.L/dr= 2.7±0.5 D/ A.
giving J.LI = 0.0419 D. This calculated value is twice the The estimated error is due entirely to the lack of knowl-
observed value of 0.0197 D.
edge of d2J.L/dr 2• The error of 0.5 D/1 is obtained from
assuming an uncertainty of ±3 D/12 for d2J.L/dr2 •
TABLE I. Observed transition frequencies and electric dipole
moments of SiO and GeO. DISCUSSION

Table II lists values of J.L. and (dJ.L/dr) IT. of CO, SiO,

Electric Transition Dipole and GeO. For CO, the sign of J.Le is known experi-
Vibrational field frequency moment
mentally,2 but only magnitudes are known for SiO and
state (V/cm) (MHz) (debye)
GeO. For CO, the dJ.L/dr is obtained from infrared ab-
ISSiO
sorption intensity measurements15 ; thus, only the mag-
0 875.88 12.8923 3.0981s
1 875.87 13.1472 3.11778
nitude is known. For SiO and GeO, the sign of dJ.L/dr
2 875.87 13.4051 3.13722 is known from this work. Of all the entries in Table
3 875.87 13.6667 3.15737 II, only J.L. of CO is small, and here the sign is known.
The signs of the other quantities are almost assuredly
7°GeO 0 590.51 9.7402 3.282~
known by comparison with calculations to be discussed
72GeO 0 590.51 9.7903 3.2823. below.
14GeO
Empirically, it is seen that there is a large (3.2 D)
0 590.51 9.8388 3.28238
1 590.51
difference in J.L. for CO and SiO, while J.L. for SiO and
10.0278 3.3032.
2 590.51 10.2191 3.3239.
GeO are quite similar. What is most surprising is the
similarity of dJ.L!dr for these three oxides.
16GeO 0 590.51 9.8850 3.2823 9 The two most complete SCF calculations for CO are
those of Hu02 and those of McLean and Yoshimine. 3 .1 6

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 3460 RA YMONDA, MUENTER, AND KLEMPERER

TABLE III. Orbital contributions to electric dipole moments in CO and SiO. All entries in atomic units."

R J.ltTtot IL-+Pr

CO

30-(C) 40-(0) 50-(C) br(O)

2.015 2.8628 0.3654 -1. 2378 -2.00 1.9904 -0.0124

2.132 3.1014 0.0378 -0.9980 -2.0320 2.1402 0.1082
2.249 3.3536 -0.3874 -0.6760 -2.0540 2.2902 0.2362

SiO

60-(Si) 50-(0) 70-(Si) 2".(0)

2.750 4.3156 -0.7444 -0.5706 -1.6648 3.0006 1.3358
2.854 4.0862 -0.7158 -0.2164 -1. 7056 3.1542 1.4486
3.104 3.2830 -0.6290 0.8572 -1. 7876 3.5112 1. 7326

" The charges on the nuclei are assigned O'+M<+. The direction of the moments is M+O-. The origins of the orbital moments are given in parentheses
f or each orbital.

They estimate that their CO and SiO calculations are
within lXlo-a and 3XIo-3 a.u. of the Hartree-Fock
limit, respectively. For CO, the calculated SCF dis-
sociation energy (SCF molecule minus SCF atoms) is
7.89 eV vs 11.42 eV observed. For SiO, the SCF dis-
sociation energy is 5.12 eV vs 8.1±0.3 eV observed.
The differences between SCF and observed De are thus
quite similar in CO and SiO.
From Table II, it is seen that the difference between
calculation and observation of P,e for both CO and SiO
is similar, being 0.39 and 0.59 D, respectively, and the
direction of the difference is the same. Similarly, the
computed dipole-moment derivatives of both CO and
SiO are twice as large as observed. This argument is
unchanged if the experimentally determined quantity
p,l is used for this comparison. As shown previously,
the value of p,l computed from the calculated values of
dp,/dr and dZp,/dr2 is twice that observed experimentally.
There appears to be a general difference between cal-
culation and observation in P,e. Assuming a sign conven-
tion in which the electric moment at distances greater
than r. is positive, the SCF value of P,e is always greater
than p,e observed. This has been noted previously for
hydrides by Huo and Cade.17 Dipole-moment deriva-
tives calculated by SCF theory are also considerably
larger than experiment. It appears likely, in view of the
quality and reproducibility of the SCF calculations,
that these discrepancies will not disappear as the
Hartree-Fock limit is reached.
For molecules such as LiH, LiF, HF, and HCI, the
origin of the discrepancy appears to arise from the im-
proper dissociation behavior of the single determinantal
function. For these systems the Hartree-Fock function
dissociates into ionic states. Presumably, even at the
equilibrium internuclear separation, too large an ionic
contribution is present in the SCF calculation. Further,
since the calculated values of dp,/ dr are much larger
than the observed, this ionic contribution increases in
importance with increasing internuclear distance as
expected_
For CO and SiO, this explanation is not adequate.
In these systems the Hartree-Fock dissociation prod-
ucts are neutral C or Si (pa2; IS+ID) and 0 (p,,4;
IS+ID) rather than CH or Si2+ and 0=.18 Although
these systems are not eigenstates of angular momentum,
they have a definite parity and therefore are nonpolar.
Thus, the nature of the inadequacy of the Hartree-
Fock model is probably more complex in CO and SiO
than in systems such as LiH.
The effect of configuration interaction on changing
the dipole moment of CO has been examined by Grim-
aldi, Lecourt, and Moser. 19 Their results gave good
agreement with experiment for p'e- On the order of 100
double and 62 single excitations were used. The single
excitations were three times as important in changing
the electric moment, while the double excitations were a
hundred times more important in changing the energy.
Their calculated value of P,e is 0.77 D with proper sign.
However, the change in dipole-moment derivative with
configuration interaction is slight. Their Hartree-Fock
value for (dp,/dr) Ire is 4.6 D/ A, while configuration
interaction reduces the value to 4_1 D/ A. It would ap-
pear that it is necessary to further investigate the dis-
tance dependence of configuration interaction more
completely.20
For both CO and SiO the SCF functions are close to
the Hartree-Fock limit. It seems unlikely that any
significant improvement in either binding energy or

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 ELECTRIC DIPOLE MOMENT OF SiO AND GeO 3461

dipole moment can be made by further SCF calcula-
tion. The SCF calculations accurately predict the differ-
ence between CO and SiO with regard to binding energy
and dipole moment. Thus, McLean and Y oshimine
functions should permit a meaningful contrast between
carbon and silicon bonding in these oxides.
Table III lists the orbital contributions to the dipole
moment of the 10 outer electrons in CO and SiO. The
other electrons are centered close enough to a nucleus
to be neglected. It is seen that no single orbital ac-
counts for the difference in moment in these two mole-
cules. Figure 1 shows the total 7r and IT moments of CO
and SiO. The IT moments fall very near a common line.
Thus, the major difference in dipole moment of CO and
3.6
3.4
3.2
SiO originates from the difference in equilibrium inter-
nuclear distance. For example, at a common distance of
2.50 a.u., the difference is 1.5 D.
It is possible in this system to examine the importance
of Si d" bonding. The 7r molecular orbitals of both oxides
are quite heteropolar; the 7r moment of Fig. 1 may be
regarded as characterizing the amount of back dona-
tion by the oxygen to the metal. It is noted first of all
that the 7r moment of SiO is smaller in magnitude than
that of CO. Examination of the McLean and Yoshi-
mine wavefunctions show that while the coefficient of
the metal atomic 3d" orbital in the highest-filled 7r
molecular orbital is twice as large in SiO as in CO, in
both instances this coefficient is small. Thus, in this one
multiple-bonded system, the d" bonding of silicon seems
unimportant. What appears to be most striking about
these two systems is the lack of any qualitative differ-
ences in their bonding.
ACKNOWLEDGMENTS
We greatly appreciate several valuable communica-
tions with Dr. A. D. McLean and Dr. M. Yoshimine.

* Supported by the U.S. Atomic Energy Commission.

3.0 1 C. A. Burrus, J. Chern. Phys. 28, 427 (1958).
2 W. M. Huo, J. Chern. Phys. 43,624 (1965).
3 A. D. McLean, M. Yoshimine, "Tables of Linear Molecule
2.8 Wavefunctions," IBM J. Res. Develop. Supp!. (to be published).
4 B. Rosenblum, A. H. Nethercot, and C. H. Townes, Phys.
Rev. lO9,400 (1958)
2.6 6 P. Kusch and V. W. Hughes, Handbw;h der Physik, S. Fliigge,
)J (o.u.) Ed. (Springer-Verlag, Berlin, 1959).
6 R. Weiss, Rev. Sci. Instr. 32,397 (1961).
7 A. Searcy, Surv. Progr. Chern. 1,35 (1963).
8 Union Carbide Corp., Carbon Products Division, New York.
sT. Tarring, Z. Naturforsch. 21A, 287 (1966).
10 T. Tarring, Z. Naturforsch. 23A, 777 (1968).
11 S. A. Rice and W. Klemperer, J. Chern. Phys. 27, 573 (1957).
12 A. Lagerqvist and U. Uhler, Arkiv Fysik 6, 95 (1953).
13 H. C. Rowlinson and R. F. Barrow, J. Chern. Phys. 21, 378
(1953).
14 T. C. James, W. G. Norris, and W. Klemperer, J. Chern.
Phys. 32, 728 (1960).
16 S. S. Penner and D. Weber, J. Chern. Phys. 19,807 (1951);
E. K. Plyler, W. S. Benedict, and S. Silverman, ibid. 20, 175
-1.6 (1952) •
16 The basis set of McLean and Yoshimine is larger (34 func-
tions) than that of Huo (24 functions). However, Huo optimized
-1.8 orbital exponents fully. The agreement between calculations is
striking, namely total energy 10-3 a.u., dipole moment 10-2 D.
17 P. E. Cade and W. M. Huo, J. Chern. Phys. 45, 1063 (1966).
18 Sheldon Green (private communication).
19 F. Grimaldi, A. Lecourt, and C. Moser, Intern. J. Quantum

2.0 22 2.4 2.6 2.8 3.0 Chern. IS, 153 (1967).

20 C. F. Bender and E. R. Davidson, J. Phys. Chern. 70,2675
R(o.u) (1966). Bender and Davidson have examined the related problem
of the dipole moment of lithium hydride and also conclude that
FIG. 1. II and". orbital contributions to the dipole moments of single excitations are more important than double excitations to
carbon monoxide and silicon monoxide. reduce the calculated value of p.. to the experimental value.

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