Relativistic four-component multiconfigurational self-consistent-field theory for molecules: Formalism

Hans Jørgen Aa Jensen*, Kenneth G. Dyall, Trond Saue, Knut Fægri

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Resumé

A formalism for relativistic four-component multiconfigurational self-consistent-field calculations on molecules is presented. The formalism parallels a direct second-order restricted-step algorithm developed for nonrelativistic molecular calculations. The presentation here focuses on the differences required by the use of the Dirac Hamiltonian with the incorporation of time-reversal symmetry and point group symmetry for D2h and subgroups, providing the expressions in this framework which correspond to the nonrelativistic expressions. It is found that an efficient algorithm requires only twice the memory used by the largest nonrelativistic calculation in the equivalent basis, due to the complex arithmetic. The feasibility of the calculations is then determined more by the disk space for storage of integrals and N-particle expansion vectors.

OriginalsprogEngelsk
TidsskriftJournal of Chemical Physics
Vol/bind104
Udgave nummer11
Sider (fra-til)4083-4097
Antal sider15
ISSN0021-9606
StatusUdgivet - 1996

Fingeraftryk

self consistent fields
formalism
Molecules
Crystal symmetry
molecules
Point groups
Hamiltonians
symmetry
subgroups
Data storage equipment
expansion

Citer dette

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abstract = "A formalism for relativistic four-component multiconfigurational self-consistent-field calculations on molecules is presented. The formalism parallels a direct second-order restricted-step algorithm developed for nonrelativistic molecular calculations. The presentation here focuses on the differences required by the use of the Dirac Hamiltonian with the incorporation of time-reversal symmetry and point group symmetry for D2h and subgroups, providing the expressions in this framework which correspond to the nonrelativistic expressions. It is found that an efficient algorithm requires only twice the memory used by the largest nonrelativistic calculation in the equivalent basis, due to the complex arithmetic. The feasibility of the calculations is then determined more by the disk space for storage of integrals and N-particle expansion vectors.",
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Relativistic four-component multiconfigurational self-consistent-field theory for molecules : Formalism. / Jensen, Hans Jørgen Aa; Dyall, Kenneth G.; Saue, Trond; Fægri, Knut.

I: Journal of Chemical Physics, Bind 104, Nr. 11, 1996, s. 4083-4097.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Relativistic four-component multiconfigurational self-consistent-field theory for molecules

T2 - Formalism

AU - Jensen, Hans Jørgen Aa

AU - Dyall, Kenneth G.

AU - Saue, Trond

AU - Fægri, Knut

PY - 1996

Y1 - 1996

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