ISSN:
1432-2234
Schlagwort(e):
Key words: Relativistic two-component quantum chemical methods
;
Complete-active-space-SCF theory
;
Spin-orbit coupling
;
Spin-dependent one-particle bases
Quelle:
Springer Online Journal Archives 1860-2000
Thema:
Chemie und Pharmazie
Notizen:
Abstract. Detailed formulae for the implementation of the multi-configuration SCF spinor optimization in a basis of Kramers pair 2-spinors – i.e. exploiting time-reversal symmetry – are presented. Full expressions for the spinor gradient and spinor Hessian elements are given in abstract form as well as within the usual CASSCF subspace division. As far as possible, the resulting terms are grouped to relativistic inactive and active Fock matrices, which have been introduced previously. Approximations for the Hessian are introduced so as to initialize it in an inverse Hessian update algorithm for a diagonal first approximation within the standard quasi-Newton-Raphson procedure. The effects of double group symmetry arising from spin dependence on Fock matrices and therefore gradient and Hessian are discussed and a group scheme for the implementation is proposed.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1007/s002140050245
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