Spin polarization in restricted electronic structure theory

Multiconfiguration self-consistent-field calculations of hyperfine coupling constants

Berta Fernandez*, Poul Jørgensen, Jørgen Byberg, Jeppe Olsen, Trygve Helgaker, Hans Jørgen Aa Jensen

*Kontaktforfatter for dette arbejde

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

It is shown that the isotropic hyperfine coupling constant Aiso associated with the Fermi contact interaction can be accurately calculated from conventional multiconfiguration self-consistent-field wave functions if, in addition to the expectation value of the contact operator, one also includes the terms originating from the response of the wave function. These response terms are nonvanishing only for perturbation operators that are nonsymmetric in spin space. Calculations of Aiso for N and BH2 illustrate the importance of the response terms and also indicate that a good estimate of the spin polarization of the core orbitals may be obtained from the response terms without correlating the core.

OriginalsprogEngelsk
TidsskriftThe Journal of Chemical Physics
Vol/bind97
Udgave nummer5
Sider (fra-til)3412-3419
Antal sider8
ISSN0021-9606
DOI
StatusUdgivet - 1. jan. 1992

Fingeraftryk

Spin polarization
Wave functions
Electronic structure
self consistent fields
electronic structure
polarization
Mathematical operators
wave functions
operators
electric contacts
orbitals
perturbation
estimates
interactions

Citer dette

@article{219578c4bb174055af025f4c98b19cb1,
title = "Spin polarization in restricted electronic structure theory: Multiconfiguration self-consistent-field calculations of hyperfine coupling constants",
abstract = "It is shown that the isotropic hyperfine coupling constant Aiso associated with the Fermi contact interaction can be accurately calculated from conventional multiconfiguration self-consistent-field wave functions if, in addition to the expectation value of the contact operator, one also includes the terms originating from the response of the wave function. These response terms are nonvanishing only for perturbation operators that are nonsymmetric in spin space. Calculations of Aiso for N and BH2 illustrate the importance of the response terms and also indicate that a good estimate of the spin polarization of the core orbitals may be obtained from the response terms without correlating the core.",
author = "Berta Fernandez and Poul J{\o}rgensen and J{\o}rgen Byberg and Jeppe Olsen and Trygve Helgaker and Jensen, {Hans J{\o}rgen Aa}",
year = "1992",
month = "1",
day = "1",
doi = "10.1063/1.462977",
language = "English",
volume = "97",
pages = "3412--3419",
journal = "The Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics",
number = "5",

}

Spin polarization in restricted electronic structure theory : Multiconfiguration self-consistent-field calculations of hyperfine coupling constants. / Fernandez, Berta; Jørgensen, Poul; Byberg, Jørgen; Olsen, Jeppe; Helgaker, Trygve; Jensen, Hans Jørgen Aa.

I: The Journal of Chemical Physics, Bind 97, Nr. 5, 01.01.1992, s. 3412-3419.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Spin polarization in restricted electronic structure theory

T2 - Multiconfiguration self-consistent-field calculations of hyperfine coupling constants

AU - Fernandez, Berta

AU - Jørgensen, Poul

AU - Byberg, Jørgen

AU - Olsen, Jeppe

AU - Helgaker, Trygve

AU - Jensen, Hans Jørgen Aa

PY - 1992/1/1

Y1 - 1992/1/1

N2 - It is shown that the isotropic hyperfine coupling constant Aiso associated with the Fermi contact interaction can be accurately calculated from conventional multiconfiguration self-consistent-field wave functions if, in addition to the expectation value of the contact operator, one also includes the terms originating from the response of the wave function. These response terms are nonvanishing only for perturbation operators that are nonsymmetric in spin space. Calculations of Aiso for N and BH2 illustrate the importance of the response terms and also indicate that a good estimate of the spin polarization of the core orbitals may be obtained from the response terms without correlating the core.

AB - It is shown that the isotropic hyperfine coupling constant Aiso associated with the Fermi contact interaction can be accurately calculated from conventional multiconfiguration self-consistent-field wave functions if, in addition to the expectation value of the contact operator, one also includes the terms originating from the response of the wave function. These response terms are nonvanishing only for perturbation operators that are nonsymmetric in spin space. Calculations of Aiso for N and BH2 illustrate the importance of the response terms and also indicate that a good estimate of the spin polarization of the core orbitals may be obtained from the response terms without correlating the core.

UR - http://www.scopus.com/inward/record.url?scp=0001269840&partnerID=8YFLogxK

U2 - 10.1063/1.462977

DO - 10.1063/1.462977

M3 - Journal article

VL - 97

SP - 3412

EP - 3419

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 5

ER -