Abstract
Results from approximate Hartree-Fock calculations on the molecules H2S and SO2 are reported. The calculations employ two contracted Gaussian functions per atomic orbital. Polarization functions have been added on all atomic centres. 3d functions on sulphur are found to be of importance for the description of the SO bond in SO2, especially through d-π backbonding. A number of molecular properties have been computed. Good agreement with experiment is obtained in all cases, where such data are available. An electron density map for the molecule SO 2 is shown, together with an electron density difference map showing the detailed effect of the 3d functions on the electron distribution.
Zusammenfassung
Für H2S und SO2 werden die Ergebnisse näherungsweiser Hartree-Fock-Rechnungen, die auf kontrahierten Sätzen von Gaußfunktionen und zusätzlichen Polarisierungsfunktionen beruhen, mitgeteilt. Es zeigt sich, daß die 3d-Funktionen für die SO-Bindung in SO2 (d-π-Rückbindung) von Wichtigkeit sind. Eine Reihe molekularer Eigenschaften wurde mit gutem Erfolg — soweit Vergleichsmaterial vorliegt — berechnet und der Einfluß der 3d-Funktionen auf die SO-Bindung mittels Elektronendichte- und -dichtedifferenz-Diagrammen veranschaulicht.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Gelius,U., Roos,B., Siegbahn,P.: Chem. Physics Letters 4, 471 (1970).
Roos,B., Siegbahn,P.: Theoret. chim. Acta (Berl.) 17, 199 (1970).
Veillard,A.: IBMOL Version IV, IBM-manual.
Moccia,R.: J. chem. Physics 40, 2186 (1964).
Rauk,A., Csizmadia,I.G.: Canad. J. Chem. 46, 1205 (1968).
Cook,D.B., Palmieri,P.: Chem. Physics Letters 3, 219 (1969).
Polezzo,S., Stabilini,M.P., Simonetta,M.: Molecular Physics 17, 1609 (1969).
Boer,F.P., Lipscomb,W.N.: J. chem. Physics 50, 989 (1969).
Hillier,I.H., Saunders,V.R.: Chem. Physics Letters 5, 384 (1970).
Rothenberg,S., Young,R.H., Shaefer,H.F.: J. Amer. chem. Soc. 92, 3243 (1970).
Edwards,T.H., Moncour,N.K., Snyder,L.E.: J. chem. Physics 46, 2139 (1967).
Roos,B., Siegbahn,P.: Theoret. chim. Acta (Berl.) 17, 209 (1970).
Huzinaga,S.: J. chem. Physics 42, 1293 (1965).
Veillard,A.: Theoret. chim. Acta (Berl.) 12, 405 (1968).
Cottrell,T.L.: The strengths of chemical bonds. London: Butterworths 1958.
Herzberg,G.: Electronic spectra of polyatomic molecules. New York: D. van Nostrand Company 1966.
Siegbahn,K., Nordling,C., Johansson,G., Hedman,I., Hedén,P.-F., Hamrin,K., Gelius,U., Bergmark,T., Werme,L.-O., Manne,R., Baer,Y.: ESCA applied to free molecules. Amsterdam: North-Holland 1969.
Rothenberg, S., Schaefer, H.F.: J. Amer. chem. Soc. in press.
Burrus,C.A., Gordy,W.: Physic. Rev. 92, 274 (1953).
McLean,A.D., Yoshimine,M.: Reported by M. Krauss, NBS Technical Note 438 (U.S. Government Printing Office, Washington, D. C. 1967).
Hillier,I.H., Saunders,V.R.: Chem. Physics Letters 4, 163 (1969).
Eland,J.H.D., Danby,C.J.: J. Mass Spectrometry and Ion Physics 1, 111 (1968).
McClellan,A.L.: Tables of experimental dipole moments. San Francisco and London: Freeman and Co 1963.
Pochan,J.M., Stone,R.G., Flygare,W.H.: J. chem. Physics 51, 4278 (1969).
Bird,G.R., Townes,C.H.: Physic. Rev. 94, 1203 (1954).
Kivelson,D.: J. chem. Physics 22, 904 (1954).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Roos, B., Siegbahn, P. MO-SCF-LCAO studies of sulphur compounds. Theoret. Chim. Acta 21, 368–380 (1971). https://doi.org/10.1007/BF00528560
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00528560