TY - JOUR

T1 - Calculation of static zero-point vibrational averaging corrections and other vibrational curvature contributions to polarizabilities and hyperpolarizabilities using field-induced coordinates

AU - Luis, Josep M.

AU - Champagne, Benoît

AU - Kirtman, Bernard

PY - 2000/11/1

Y1 - 2000/11/1

N2 - 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 3N-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 NH2-(CH = CH)3-NO2. 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 NH2(CH = CH)3NO2 at the Hartree-Fock/6-31G+p level. Including electron correlation at the second-order Moller-Plesset (MP2) level, and the frequency dependence of the ZPVA correction is discussed.

AB - 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 3N-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 NH2-(CH = CH)3-NO2. 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 NH2(CH = CH)3NO2 at the Hartree-Fock/6-31G+p level. Including electron correlation at the second-order Moller-Plesset (MP2) level, and the frequency dependence of the ZPVA correction is discussed.

UR - http://www.scopus.com/inward/record.url?scp=0034325104&partnerID=8YFLogxK

U2 - 10.1002/1097-461X(2000)80:3<471::AID-QUA17>3.0.CO;2-B

DO - 10.1002/1097-461X(2000)80:3<471::AID-QUA17>3.0.CO;2-B

M3 - Article

AN - SCOPUS:0034325104

VL - 80

SP - 471

EP - 479

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 3

ER -