TIME-DEPENDENT HARTREE-FOCK 2ND-ORDER MOLECULAR-PROPERTIES WITH A MODERATELY SIZED BASIS SET .1. THE FREQUENCY-DEPENDENCE OF THE DIPOLE POLARIZABILITY

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Abstract

Time-dependent coupled Hartree-Fock calculations of the frequency-dependent mean polarizability alpha-(omega) and its anisotropy DELTA-alpha-(omega) are presented for a wide range of molecules containing first and second row atoms. The Cauchy moments S(-2) and S(-4), which describe the dispersion in alpha-(omega), are systematically underestimated by 20% and 40%, respectively, with the 6-31G(+ sd + sp) basis set. The dispersion in DELTA-alpha-(omega) is also underestimated, typically by 50%. Many exceptions to this behavior are observed, most of which appear to be an underestimate of the experimental dispersion in DELTA-alpha-(omega) by a greater amount. This seems to be the result of systematic experimental overestimates of dispersion in DELTA-alpha-(omega) for molecules with very small Rayleigh depolarization ratios (rho-0 <10(-2)), suggesting that the vibrational Raman contribution in these experiments is not only important, but significantly frequency dependent.

Original languageEnglish
Pages (from-to)1288-1294
Number of pages7
JournalJournal of Chemical Physics
Volume94
Issue number2
DOIs
Publication statusPublished - 15 Jan 1991
Externally publishedYes

Cite this

@article{f5a900714c344a39b93061bf8ec0697c,
title = "TIME-DEPENDENT HARTREE-FOCK 2ND-ORDER MOLECULAR-PROPERTIES WITH A MODERATELY SIZED BASIS SET .1. THE FREQUENCY-DEPENDENCE OF THE DIPOLE POLARIZABILITY",
abstract = "Time-dependent coupled Hartree-Fock calculations of the frequency-dependent mean polarizability alpha-(omega) and its anisotropy DELTA-alpha-(omega) are presented for a wide range of molecules containing first and second row atoms. The Cauchy moments S(-2) and S(-4), which describe the dispersion in alpha-(omega), are systematically underestimated by 20{\%} and 40{\%}, respectively, with the 6-31G(+ sd + sp) basis set. The dispersion in DELTA-alpha-(omega) is also underestimated, typically by 50{\%}. Many exceptions to this behavior are observed, most of which appear to be an underestimate of the experimental dispersion in DELTA-alpha-(omega) by a greater amount. This seems to be the result of systematic experimental overestimates of dispersion in DELTA-alpha-(omega) for molecules with very small Rayleigh depolarization ratios (rho-0 <10(-2)), suggesting that the vibrational Raman contribution in these experiments is not only important, but significantly frequency dependent.",
keywords = "OSCILLATOR-STRENGTH DISTRIBUTIONS, DISPERSION ENERGY COEFFICIENTS, MULTICONFIGURATIONAL LINEAR RESPONSE, POLARIZATION PROPAGATOR APPROACH, FIELD METHOD CALCULATIONS, DYNAMIC POLARIZABILITIES, ABINITIO CALCULATION, PERTURBATION-THEORY, MULTIPOLE MOMENTS, ORBITAL METHODS",
author = "Mark Spackman",
year = "1991",
month = "1",
day = "15",
doi = "10.1063/1.460038",
language = "English",
volume = "94",
pages = "1288--1294",
journal = "The Journal of Chemical Physics",
issn = "0021-9606",
publisher = "ACOUSTICAL SOC AMER AMER INST PHYSICS",
number = "2",

}

TY - JOUR

T1 - TIME-DEPENDENT HARTREE-FOCK 2ND-ORDER MOLECULAR-PROPERTIES WITH A MODERATELY SIZED BASIS SET .1. THE FREQUENCY-DEPENDENCE OF THE DIPOLE POLARIZABILITY

AU - Spackman, Mark

PY - 1991/1/15

Y1 - 1991/1/15

N2 - Time-dependent coupled Hartree-Fock calculations of the frequency-dependent mean polarizability alpha-(omega) and its anisotropy DELTA-alpha-(omega) are presented for a wide range of molecules containing first and second row atoms. The Cauchy moments S(-2) and S(-4), which describe the dispersion in alpha-(omega), are systematically underestimated by 20% and 40%, respectively, with the 6-31G(+ sd + sp) basis set. The dispersion in DELTA-alpha-(omega) is also underestimated, typically by 50%. Many exceptions to this behavior are observed, most of which appear to be an underestimate of the experimental dispersion in DELTA-alpha-(omega) by a greater amount. This seems to be the result of systematic experimental overestimates of dispersion in DELTA-alpha-(omega) for molecules with very small Rayleigh depolarization ratios (rho-0 <10(-2)), suggesting that the vibrational Raman contribution in these experiments is not only important, but significantly frequency dependent.

AB - Time-dependent coupled Hartree-Fock calculations of the frequency-dependent mean polarizability alpha-(omega) and its anisotropy DELTA-alpha-(omega) are presented for a wide range of molecules containing first and second row atoms. The Cauchy moments S(-2) and S(-4), which describe the dispersion in alpha-(omega), are systematically underestimated by 20% and 40%, respectively, with the 6-31G(+ sd + sp) basis set. The dispersion in DELTA-alpha-(omega) is also underestimated, typically by 50%. Many exceptions to this behavior are observed, most of which appear to be an underestimate of the experimental dispersion in DELTA-alpha-(omega) by a greater amount. This seems to be the result of systematic experimental overestimates of dispersion in DELTA-alpha-(omega) for molecules with very small Rayleigh depolarization ratios (rho-0 <10(-2)), suggesting that the vibrational Raman contribution in these experiments is not only important, but significantly frequency dependent.

KW - OSCILLATOR-STRENGTH DISTRIBUTIONS

KW - DISPERSION ENERGY COEFFICIENTS

KW - MULTICONFIGURATIONAL LINEAR RESPONSE

KW - POLARIZATION PROPAGATOR APPROACH

KW - FIELD METHOD CALCULATIONS

KW - DYNAMIC POLARIZABILITIES

KW - ABINITIO CALCULATION

KW - PERTURBATION-THEORY

KW - MULTIPOLE MOMENTS

KW - ORBITAL METHODS

U2 - 10.1063/1.460038

DO - 10.1063/1.460038

M3 - Article

VL - 94

SP - 1288

EP - 1294

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 2

ER -