Relativistic corrections to molecular dynamic dipole polarizabilities

Sheela Kirpekar*, Jens Oddershede, Hans Jørgen Aagaard Jensen

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Resumé

Using response function methods we report calculations of the dynamic isotropic polarizability of SnH4 and PbH4 and of the relativistic corrections to it in the random phase approximation and at the correlated multiconfigurational linear response level of approximation. All relativistic corrections obtained from the use of the Darwin and mass-velocity operators to first order are included at both levels of approximation. We find that correlation and relativistic contributions are not even approximately additive for the two molecules. The importance of the relativistic corrections is smallest in the correlated calculations, as has also been observed for other properties. For SnH4 the correlation contribution and the pure relativistic correction are of the same order of magnitude, whereas for PbH 4 the relativistic correction becomes more important than the correlation contribution. We report estimated Cauchy moments, obtained from fitting the dispersion of the calculated corrections as a function of ω2. The frequency dependence of the nonrelativistic polarizability is most pronounced at the correlated level, mainly due to lower excitation energies in the multiconfigurational calculations than those in the random phase approximation.

OriginalsprogEngelsk
TidsskriftThe Journal of Chemical Physics
Vol/bind103
Udgave nummer8
Sider (fra-til)2983-2990
Antal sider8
ISSN0021-9606
StatusUdgivet - 1995

Fingeraftryk

Molecular dynamics
dipoles
molecular dynamics
Excitation energy
approximation
Molecules
moments
operators
excitation
molecules
energy

Citer dette

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abstract = "Using response function methods we report calculations of the dynamic isotropic polarizability of SnH4 and PbH4 and of the relativistic corrections to it in the random phase approximation and at the correlated multiconfigurational linear response level of approximation. All relativistic corrections obtained from the use of the Darwin and mass-velocity operators to first order are included at both levels of approximation. We find that correlation and relativistic contributions are not even approximately additive for the two molecules. The importance of the relativistic corrections is smallest in the correlated calculations, as has also been observed for other properties. For SnH4 the correlation contribution and the pure relativistic correction are of the same order of magnitude, whereas for PbH 4 the relativistic correction becomes more important than the correlation contribution. We report estimated Cauchy moments, obtained from fitting the dispersion of the calculated corrections as a function of ω2. The frequency dependence of the nonrelativistic polarizability is most pronounced at the correlated level, mainly due to lower excitation energies in the multiconfigurational calculations than those in the random phase approximation.",
author = "Sheela Kirpekar and Jens Oddershede and Jensen, {Hans J{\o}rgen Aagaard}",
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Relativistic corrections to molecular dynamic dipole polarizabilities. / Kirpekar, Sheela; Oddershede, Jens; Jensen, Hans Jørgen Aagaard.

I: The Journal of Chemical Physics, Bind 103, Nr. 8, 1995, s. 2983-2990.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Relativistic corrections to molecular dynamic dipole polarizabilities

AU - Kirpekar, Sheela

AU - Oddershede, Jens

AU - Jensen, Hans Jørgen Aagaard

PY - 1995

Y1 - 1995

N2 - Using response function methods we report calculations of the dynamic isotropic polarizability of SnH4 and PbH4 and of the relativistic corrections to it in the random phase approximation and at the correlated multiconfigurational linear response level of approximation. All relativistic corrections obtained from the use of the Darwin and mass-velocity operators to first order are included at both levels of approximation. We find that correlation and relativistic contributions are not even approximately additive for the two molecules. The importance of the relativistic corrections is smallest in the correlated calculations, as has also been observed for other properties. For SnH4 the correlation contribution and the pure relativistic correction are of the same order of magnitude, whereas for PbH 4 the relativistic correction becomes more important than the correlation contribution. We report estimated Cauchy moments, obtained from fitting the dispersion of the calculated corrections as a function of ω2. The frequency dependence of the nonrelativistic polarizability is most pronounced at the correlated level, mainly due to lower excitation energies in the multiconfigurational calculations than those in the random phase approximation.

AB - Using response function methods we report calculations of the dynamic isotropic polarizability of SnH4 and PbH4 and of the relativistic corrections to it in the random phase approximation and at the correlated multiconfigurational linear response level of approximation. All relativistic corrections obtained from the use of the Darwin and mass-velocity operators to first order are included at both levels of approximation. We find that correlation and relativistic contributions are not even approximately additive for the two molecules. The importance of the relativistic corrections is smallest in the correlated calculations, as has also been observed for other properties. For SnH4 the correlation contribution and the pure relativistic correction are of the same order of magnitude, whereas for PbH 4 the relativistic correction becomes more important than the correlation contribution. We report estimated Cauchy moments, obtained from fitting the dispersion of the calculated corrections as a function of ω2. The frequency dependence of the nonrelativistic polarizability is most pronounced at the correlated level, mainly due to lower excitation energies in the multiconfigurational calculations than those in the random phase approximation.

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