Magnetic shielding constants calculated by the infinite-order Douglas-Kroll-Hess method with electron-electron relativistic corrections

Junji Seino, Masahiko Hada

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

We presented a two-component relativistic quantum-chemical theory for magnetic shielding constants, which is based on the infinite-order Douglas-Kroll (IODK) transformation. Two-electron relativistic corrections were also generated using the IODK transformation, although negligibly small terms were discarded. The use of small-component basis functions was completely excluded from the present theory. We examined the combination of the levels of relativistic one- and two-electron terms and magnetic interaction terms using the first-order Foldy-Wouthuysen (FW1), the second-order Douglas-Kroll (DK2), and the infinite-order Douglas-Kroll (IODK) transformations, as well as the lowest-order (c-2) Breit-Pauli approximation. We calculated the magnetic shielding constants of several closed-shell atoms using the FW1, DK2, IODK, and Breit-Pauli Hamiltonians. The IODK Hamiltonian reproduced well the results calculated by the four-component Dirac-Fock-Coulomb theory: The maximum deviation is only about 2.2%. We found that the accuracy of the magnetic shielding constants is strongly affected by the relativistic treatments of one-electron magnetic interaction, while the effect of the two-component two-electron relativistic corrections is relatively small. We also discussed the picture change effect on magnetic operators.

Original languageEnglish
Article number174105
JournalJournal of Chemical Physics
Volume132
Issue number17
DOIs
Publication statusPublished - 2010 May 7
Externally publishedYes

Fingerprint

Magnetic shielding
magnetic shielding
Electrons
Hamiltonians
electrons
interactions
deviation
operators
Atoms
approximation
atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

@article{92737cca0e674a66a8bc6d599313dcad,
title = "Magnetic shielding constants calculated by the infinite-order Douglas-Kroll-Hess method with electron-electron relativistic corrections",
abstract = "We presented a two-component relativistic quantum-chemical theory for magnetic shielding constants, which is based on the infinite-order Douglas-Kroll (IODK) transformation. Two-electron relativistic corrections were also generated using the IODK transformation, although negligibly small terms were discarded. The use of small-component basis functions was completely excluded from the present theory. We examined the combination of the levels of relativistic one- and two-electron terms and magnetic interaction terms using the first-order Foldy-Wouthuysen (FW1), the second-order Douglas-Kroll (DK2), and the infinite-order Douglas-Kroll (IODK) transformations, as well as the lowest-order (c-2) Breit-Pauli approximation. We calculated the magnetic shielding constants of several closed-shell atoms using the FW1, DK2, IODK, and Breit-Pauli Hamiltonians. The IODK Hamiltonian reproduced well the results calculated by the four-component Dirac-Fock-Coulomb theory: The maximum deviation is only about 2.2{\%}. We found that the accuracy of the magnetic shielding constants is strongly affected by the relativistic treatments of one-electron magnetic interaction, while the effect of the two-component two-electron relativistic corrections is relatively small. We also discussed the picture change effect on magnetic operators.",
author = "Junji Seino and Masahiko Hada",
year = "2010",
month = "5",
day = "7",
doi = "10.1063/1.3413529",
language = "English",
volume = "132",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "17",

}

TY - JOUR

T1 - Magnetic shielding constants calculated by the infinite-order Douglas-Kroll-Hess method with electron-electron relativistic corrections

AU - Seino, Junji

AU - Hada, Masahiko

PY - 2010/5/7

Y1 - 2010/5/7

N2 - We presented a two-component relativistic quantum-chemical theory for magnetic shielding constants, which is based on the infinite-order Douglas-Kroll (IODK) transformation. Two-electron relativistic corrections were also generated using the IODK transformation, although negligibly small terms were discarded. The use of small-component basis functions was completely excluded from the present theory. We examined the combination of the levels of relativistic one- and two-electron terms and magnetic interaction terms using the first-order Foldy-Wouthuysen (FW1), the second-order Douglas-Kroll (DK2), and the infinite-order Douglas-Kroll (IODK) transformations, as well as the lowest-order (c-2) Breit-Pauli approximation. We calculated the magnetic shielding constants of several closed-shell atoms using the FW1, DK2, IODK, and Breit-Pauli Hamiltonians. The IODK Hamiltonian reproduced well the results calculated by the four-component Dirac-Fock-Coulomb theory: The maximum deviation is only about 2.2%. We found that the accuracy of the magnetic shielding constants is strongly affected by the relativistic treatments of one-electron magnetic interaction, while the effect of the two-component two-electron relativistic corrections is relatively small. We also discussed the picture change effect on magnetic operators.

AB - We presented a two-component relativistic quantum-chemical theory for magnetic shielding constants, which is based on the infinite-order Douglas-Kroll (IODK) transformation. Two-electron relativistic corrections were also generated using the IODK transformation, although negligibly small terms were discarded. The use of small-component basis functions was completely excluded from the present theory. We examined the combination of the levels of relativistic one- and two-electron terms and magnetic interaction terms using the first-order Foldy-Wouthuysen (FW1), the second-order Douglas-Kroll (DK2), and the infinite-order Douglas-Kroll (IODK) transformations, as well as the lowest-order (c-2) Breit-Pauli approximation. We calculated the magnetic shielding constants of several closed-shell atoms using the FW1, DK2, IODK, and Breit-Pauli Hamiltonians. The IODK Hamiltonian reproduced well the results calculated by the four-component Dirac-Fock-Coulomb theory: The maximum deviation is only about 2.2%. We found that the accuracy of the magnetic shielding constants is strongly affected by the relativistic treatments of one-electron magnetic interaction, while the effect of the two-component two-electron relativistic corrections is relatively small. We also discussed the picture change effect on magnetic operators.

UR - http://www.scopus.com/inward/record.url?scp=78049360083&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=78049360083&partnerID=8YFLogxK

U2 - 10.1063/1.3413529

DO - 10.1063/1.3413529

M3 - Article

VL - 132

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

M1 - 174105

ER -