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Dipole (electric field) and quadrupole (field gradient) polarizabilities of hydrogen, nitrogen, and acetylene from the application of derivative Hartree--Fock theory

Journal Article · · J. Chem. Phys.; (United States)
DOI:https://doi.org/10.1063/1.448852· OSTI ID:6025222
The electrical polarizabilities of a molecule are of potential importance in the molecule's response to an applied field or in the interaction with other proximate molecules. Derivative Hartree--Fock (DHF) theory, which is an open-ended, uniform procedure for calculating properties corresponding to derivatives of the electronic energy, has been applied in obtaining electrical polarizabilities of hydrogen, nitrogen, and acetylene. In order to provide a more complete description than previously available, this has been carried through the third level of differentiation with respect to electric field and field gradient components, thereby yielding dipole and quadrupole hyperpolarizabilities. Extensive basis set tests performed on hydrogen reinforce the established need for extended sets with diffuse functions, and for balance in the flexibility of the s, p, d,...type functions on each center. DHF is well suited to the use of such large basis sets and in the case of acetylene, a basis of 100 functions was used to calculate its electrical properties.
Research Organization:
School of Chemical Sciences, University of Illinois, Urbana, Illinois 61801
OSTI ID:
6025222
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 82:9; ISSN JCPSA
Country of Publication:
United States
Language:
English