Abstract
With aid of the virial theorem formulated for the energy differences of two electronic states some theorems on the wave functions of diatomic molecules have been proven. It is shown how proper Rydberg states can be distinguished from other electronic states with a diffuse outer orbital by virtue of the virial theorem and that a singlet-triplet pair of excited states cannot have the same equilibrium geometry and identical orbitals simultaneously. Furthermore if the two states have the same dissociation limit a theorem on the differences of the kinetic and the potential energy can be derived which allows an understanding of the shape of the electronic wave functions. As an application the wave functions and the ordering of the lowest states of H +2 and H2 have been discussed.
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References
Lemberger,A., Pauncz,R.: Acta Phys. Hung.27, 169 (1969)
Messmer,R.P., Birss,F.W.: J. Phys. Chem.73, 2085 (1969)
Colpa,J.P., Islip,M.F.J.: Mol. Phys.25, 701 (1973)
Katriel,J.: Theoret. Chim. Acta (Berl.)23, 309 (1972)
Katriel,J.: Phys. Rev.A5, 1990 (1972)
Killingbeck,J.: Mol. Phys.25, 455 (1973)
Colpa,J.P., Brown,R.E.: Mol. Phys.26, 1453 (1973)
Colpa,J.P.: Mol. Phys.28, 581 (1974)
Ahlrichs,R.: Chem. Phys. Letters15, 609 (1972)
Ahlrichs,R.: Chem. Phys. Letters18, 521 (1973)
Ahlrichs,R.: J. Math. Phys.14, 1860 (1973)
Hellmann,H.: Z. Phys.35, 180 (1933)
Slater,J.C.: J. Chem. Phys.1, 687 (1933)
Ruedenberg,K.: Rev. Mod. Phys.34, 326 (1962)
Feinberg,M.J., Ruedenberg,K., Mehler,E.L.: Advan. Quantum Chem.5, 27 (1970);
Feinberg,M.J., Ruedenberg,K.: J. Chem. Phys.54, 1495 (1971)
Kolos,W., Wolniewicz,L.: J. Chem. Phys.43, 2429 (1965)
Merer,A.J., Mulliken,R.S.: Chem. Rev.69, 639 (1969)
Bowman,J.D., Hirschfelder,J.O., Wahl,A.C.: J. Chem. Phys.53, 2743 (1970)
Mulliken,R.S.: J. Am. Chem. Soc.86, 3183 (1964)
Accad,Y., Pekeris,C.L., Schiff,B.: Phys. Rev.A4, 516 (1971)
Boyd,R.J., Coulson,C.A.: J. Phys.B6, 782 (1972)
Beckel,C.L., Hansen,B.D., Peek,J.M.: J. Chem. Phys.53, 3681 (1970)
Hurley,A.C., in: Molecular orbitals in chemistry, physics and biology, Löwdin, P.O., Pullman, B. Eds. New York: Academic Press 1964
Bates,D.R., Ledsham,K., Stewart,A.L.: Phil. Trans. Roy. Soc. (London)A246, 215 (1954)
Jungen,M.: Theoret. Chim. Acta (Berl.)27, 33 (1972)
Heitler,W., London,F.: Z. Phys.44, 455 (1927)
Wang,S.: Phys. Rev.31, 579 (1928)
Coulson,C.A.: Trans. Faraday Soc.33, 1479 (1973)
Bingel,W.A., Preuss,H., Schmidtke,H.H.: Z. Naturforsch.16a, 434 (1961)
Bingel,W.A., Hinkelmann,H., Koch,R.J.: Chem. Phys. Letters1, 251, 427 (1967)
Lieb,E., Mattis,D.: Phys. Rev.125, 164 (1962)
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This work is part of the project Nr. SR 2.159.74 of the “Schweizerischer Nationalfonds”.
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Jungen, M. Application of the virial theorem to the study of molecular electronic wave functions. Theoret. Chim. Acta 41, 51–58 (1976). https://doi.org/10.1007/BF00558023
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DOI: https://doi.org/10.1007/BF00558023