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Calculations of molecular polarizabilities from electric‐field‐variant atomic orbitals: An analysis of the problem and its application to the hydrogen molecule and to the alkane series
Author(s) -
Andre J. M.,
Delhalle J.,
Fripiat J. G.,
Hennico G.,
Piela L.
Publication year - 1988
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560340868
Subject(s) - atomic orbital , molecular orbital , electric field , gaussian , series (stratigraphy) , slater type orbital , alkane , molecular orbital theory , field (mathematics) , chemistry , molecule , computational chemistry , atomic physics , molecular physics , physics , quantum mechanics , mathematics , hydrocarbon , electron , paleontology , organic chemistry , biology , pure mathematics
This paper analyzes the use of electric‐field‐variant ( EFV ) atomic orbitals in calculations of molecular polarizabilities using the finite field approximation. It is shown that, in the absence of an external electric field, the optimal positions of the orbital centers which minimize the total energy are already shifted with respect to the atomic sites and that these optimal positions constitute a better starting point to compute molecular polarizabilities by the finite field method. The technique is applied to the hydrogen molecule and to the alkane series C n H 2 n +2 , n = 1, 2, 3, 4, 5, 6 in the framework of a floating spherical gaussian orbital‐ EFV basis.