The generalized active space concept for the relativistic treatment of electron correlation. II. Large-scale configuration interaction implementation based on relativistic 2- and 4-spinors and its application
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- Timo Fleig
- Department of Theoretical Chemistry, Faculty of Sciences, Free University of Amsterdam, De Boelelaan 1083, NL-1081 HV Amsterdam, The Netherlands
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- Jeppe Olsen
- Theoretical Chemistry, Langelandsgade 140, University of Århus, DK-8000 Århus C, Denmark
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- Lucas Visscher
- Department of Theoretical Chemistry, Faculty of Sciences, Free University of Amsterdam, De Boelelaan 1083, NL-1081 HV Amsterdam, The Netherlands
抄録
<jats:p>The extension of a relativistic double group configuration interaction (CI) formalism to the use of 2- and 4-spinors is presented. We first elucidate the theoretical aspects of the formalism that is needed to work with spinors that are optimized with a Hartree–Fock scheme that includes spin–orbit coupling. We then describe a new general implementation for the computation of sigma vectors and n-particle density matrices that occur in direct CI algorithms. Sample calculations of the spin–orbit splitting in atoms with one particle or hole in an otherwise closed shell configuration l1 (l=1,2,3) and molecules containing such atoms illustrate the advantage of treating this effect in a basis of true spinors rather than in a basis of scalar relativistic orbitals as is conventionally done.</jats:p>
収録刊行物
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- The Journal of Chemical Physics
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The Journal of Chemical Physics 119 (6), 2963-2971, 2003-08-08
AIP Publishing