Abstract
The idea of the basis set polarization which follows from the known dependence of basis set functions on the perturbation strength is applied to the calculation of the dipole moment derivatives with respect to nuclear displacements. The differentiation of the dipole moment function is replaced by the straightforward evaluation of derivatives of the intramolecular electric field with respect to the external electric field strength. The method and its efficiency are illustrated by a series of calculations of the dipole moment derivatives for the water molecule. Already a polarized basis set of 26 CGTO's derived from the minimal CGTO basis set provides fairly reasonable results.
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References
Steele, D., Person, W. B. In: Specialist Periodical Report. Molecular Spectroscopy. Vol. 2, pp. 357–438. London: Chemical Society 1975; see also recent reviews in: Vibrational Intensities in Infrared and Raman Spectroscopy. Person, W. B., Zerbi, G. (eds.) Amsterdam: Elsevier 1982
Steele, D.: Adv. IR Raman Spectrosc. 1, 232 (1975)
John, I. G., Bacskay, G., Hush, N. S.: Chem. Phys. 51, 49 (1980) and references therein
Komornicki, A., McIver Jr., J. W.: J. Chem. Phys. 70, 2014 (1979); Komornicki, A., Jaffe, R. L.: J. Chem. Phys. 71, 2150 (1979); Carlowitz von, S., Ziel, W., Pulay, P., Boggs, J. E.: J. Mol. Struct. Teochem. 87, 113 (1982): Fredkin, D. R., Komornicki, A., White, S. R., Wilson, K. R.: J. Chem. Phys. 78, 7077 (1983)
Bacskay, G. B., Saebø, S., Taylor, P. R.: Chem. Phys. in the press
Pulay, P. In: Schaefer III, H. F. (ed.), Applications of Molecular Electronic Structure Theory, New York: Plenum Press 1977; Pulay, P.: J. Chem. Phys. 78, 5043 (1983)
Swanstrøm, P., Hegelund, F. In: Diercksen, G. H. F., Sutcliffe, B. T., Veillard, A. (eds.), Computational Techniques in Quantum Chemistry and Molecular Physics, p. 299. Dordrecht: Reidel Publ. Co. 1975
Lazzeretti, P., Zanasi, R.: Chem. Phys. Letters 112, 103 (1984)
Lazzeretti, P., Zanasi, R.: Chem. Phys. Letters 71, 529 (1980); Lazzeretti, P., Zanasi, R.: J. Chem. Phys., to be published
Lazzeretti, P., Zanasi, R.: Phys. Rev. A24, 1696 (1981)
Roos, B. O., Sadlej, A. J.: Chem. Phys., 94 43 (1985)
Biarge, J. F., Herranz, J., Morcillo, J.: An. R. Soc. Esp. Fis. Quim. Ser. A57, 81 (1961); Morcillo, L. J., Zamorano, J., Heredia, J. M. V.: Spectrochim. Acta 22, 1969 (1966).
Person, W. B., Newton, J. H.: J. Chem. Phys. 61, 1040 (1974); Person, W. B., Newton, J. H.: J. Chem. Phys. 64, 3036 (1976)
Epstein, S. T.: The Variation Method in Quantum Chemistry. New York: Academic Press 1974
Hirschfelder, J. O., Epstein, S. T., Byers-Brown, W.: Adv. Quantum Chem. 1, 284 (1964).
Gerrat, J., Mills, I. M.: J. Chem. Phys. 49, 1719, 1730 (1968); Thomson, K., Swanstrøm, P.: Mol. Phys. 26, 735, 751 (1974)
Dodds, J. L., McWeeny, R., Sadlej, A. J.: Mol. Phys. 34, 1779 (1977)
Epstein, S. T., Sadlej, A. J.: Int. J. Quantum Chem. 15, 147 (1979); Woliński, K., Sadlej, A. J.: Mol. Phys. 41, 1419 (1980)
Nerbrant, P.-O., Roos, B. O., Sadlej, A. J.: Int. J. Quantum Chem. 15, 135 (1979); Diercksen, G. H. F., Roos, B. O., Sadlej, A. J.: Chem. Phys. 59, 29 (1981)
Dalgarno, A.: Adv. Phys. 11, 281 (1962)
Roos, B., Siegbahn, P.: Theoret. Chim. Acta (Berl.) 17, 209 (1970)
Huzinaga, S.: J. Chem. Phys. 42, 1293 (1965)
Snyder, L. C., Basch, H.: Molecular Wave Functions and Properties. New York: Wiley 1972
Huzinaga, S.: Approximate Atomic Functions. Technical Report: Division of Theoretical Chemistry, Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada 1971
Salez, C., Veillard, A.: Theoret. Chim. Acta (Berl.) 11, 441 (1968)
Sadlej, A. J.: Mol. Phys. 34, 731 (1977)
Dunning Jr., T. H., Hay, P. J. In: Methods of Electronic Structure Theory, Vol. 3, p. 1. H. F. Schaefer III, (ed.) New York: Plenum Press 1977
Zilles, B. A., Person, W. B.; J. Chem. Phys. 79, 65 (1983)
Nakatsuji, H., Kanda, K., Yonezawa, T.; J. Chem. Phys. 77, 3109 (1982)
Sadlej, A. J.: Acta Phys. Polon. A53, 297 (1978)
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Wolinski, K., Roos, B.O. & Sadlej, A.J. Polarized basis sets and the calculation of infrared intensities from nuclear electric shielding tensors. Theoret. Chim. Acta 68, 431–444 (1985). https://doi.org/10.1007/BF00527668
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DOI: https://doi.org/10.1007/BF00527668