An analytic method to evaluate nuclear contributions to electrical properties of polyatomic molecules is presented. Such contributions control changes induced by an electric field on equilibrium geometry (nuclear relaxation contribution) and vibrational motion (vibrational contribution) of a molecular system. Expressions to compute the nuclear contributions have been derived from a power series expansion of the potential energy. These contributions to the electrical properties are given in terms of energy derivatives with respect to normal coordinates, electric field intensity or both. Only one calculation of such derivatives at the field-free equilibrium geometry is required. To show the useful efficiency of the analytical evaluation of electrical properties (the so-called AEEP method), results for calculations on water and pyridine at the SCF/TZ2P and the MP2/TZ2P levels of theory are reported. The results obtained are compared with previous theoretical calculations and with experimental values.
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1 August 1997
Research Article|
August 01 1997
A systematic and feasible method for computing nuclear contributions to electrical properties of polyatomic molecules
Josep M. Luis;
Josep M. Luis
Institute of Computational Chemistry, Department of Chemistry, University of Girona, 17017 Girona (Catalonia), Spain
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Miquel Duran;
Miquel Duran
Institute of Computational Chemistry, Department of Chemistry, University of Girona, 17017 Girona (Catalonia), Spain
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José L. Andrés
José L. Andrés
Institute of Computational Chemistry, Department of Chemistry, University of Girona, 17017 Girona (Catalonia), Spain
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J. Chem. Phys. 107, 1501–1512 (1997)
Article history
Received:
November 25 1996
Accepted:
April 24 1997
Citation
Josep M. Luis, Miquel Duran, José L. Andrés; A systematic and feasible method for computing nuclear contributions to electrical properties of polyatomic molecules. J. Chem. Phys. 1 August 1997; 107 (5): 1501–1512. https://doi.org/10.1063/1.474503
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