### 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 D_{2h} 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.

Originalsprog | Engelsk |
---|---|

Tidsskrift | Journal of Chemical Physics |

Vol/bind | 104 |

Udgave nummer | 11 |

Sider (fra-til) | 4083-4097 |

Antal sider | 15 |

ISSN | 0021-9606 |

Status | Udgivet - 1996 |

### Fingeraftryk

### Citer dette

*Journal of Chemical Physics*,

*104*(11), 4083-4097.

}

*Journal of Chemical Physics*, bind 104, nr. 11, s. 4083-4097.

**Relativistic four-component multiconfigurational self-consistent-field theory for molecules : Formalism.** / Jensen, Hans Jørgen Aa; Dyall, Kenneth G.; Saue, Trond; Fægri, Knut.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer 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

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0346077297&partnerID=8YFLogxK

M3 - Journal article

AN - SCOPUS:0346077297

VL - 104

SP - 4083

EP - 4097

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 11

ER -