Breakdown of the Born-Oppenheimer Approximation in the Calculation of Electric Hyperpolarizabilities

David M. Bishop and Sasha A. Solunac
Phys. Rev. Lett. 55, 1986 – Published 4 November 1985; Erratum Phys. Rev. Lett. 55, 2627 (1985)
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Abstract

For the first time a nonadiabatic (all-particle) calculation has been carried out for the electric polarizabilities and hyperpolarizabilities of H2+, HD+, and D2+ in their lowest rovibronic states. The value of the hyperpolarizability γ is dramatically different from that which would be assumed from calculations based on the Born-Oppenheimer approximation unless account is taken of a vibrational contribution which (unlike its counterpart for the α polarizability) is nonzero even for a homonuclear diatomic molecule. For H2+ we find that αzz=5.827 a.u. and γzzz=2.2×103 a.u.

  • Received 1 August 1985

DOI:https://doi.org/10.1103/PhysRevLett.55.1986

©1985 American Physical Society

Erratum

Non-Born-Oppenheimer Calculation of Electric Hyperpolarizabilities

David M. Bishop and Sasha A. Solunac
Phys. Rev. Lett. 55, 2627 (1985)

Authors & Affiliations

David M. Bishop* and Sasha A. Solunac

  • Department of Chemistry, University of Ottawa, Ottawa, Ontario, KIN 9B4, Canada

  • *Member of the Ottawa-Carleton Chemistry Institute; to whom all correspondence should be addressed.

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Issue

Vol. 55, Iss. 19 — 4 November 1985

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