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Calculation of static zero‐point vibrational averaging corrections and other vibrational curvature contributions to polarizabilities and hyperpolarizabilities using field‐induced coordinates
Author(s) -
Luis Josep M.,
Champagne Benoît,
Kirtman Bernard
Publication year - 2000
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 - 10.1002/1097-461x(2000)80:3<471::aid-qua17>3.0.co;2-b
Subject(s) - polarizability , zero point energy , curvature , chemistry , zero (linguistics) , normal coordinates , field (mathematics) , electric field , atomic physics , computational chemistry , physics , quantum mechanics , mathematics , geometry , molecule , pure mathematics , organic chemistry , linguistics , philosophy
The zero‐point static vibrational averaging (ZPVA) correction to the (hyper)polarizability is written in first‐order as the sum of two contributions, one involving electric field derivatives and the other a sum over normal coordinate derivatives of the zero‐point energy. It is shown that the sum over 3 N −6 normal modes can be replaced by a single term using field‐induced coordinates (FICs). A computational strategy that takes advantage of this simplification is presented and applied to a typical push–pull polyene NH 2 (CHCH) 3 NO 2 . From the dependence of the first‐order ZPVA on the field‐dependent equilibrium geometry, we also obtain other low‐order static and dynamic vibrational curvature contributions to the (hyper)polarizabilities. The entire set of electronic and vibrational terms is partitioned into two different sequences, each of which exhibits rapid initial convergence for NH 2 (CHCH) 3 NO 2 at the Hartree–Fock/6‐31G+p level. Including electron correlation at the second‐order Møller–Plesset (MP2) level, and the frequency dependence of the ZPVA correction is discussed. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 471–479, 2000