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Correlated response calculations of the spin–orbit interaction contribution to nuclear spin–spin couplings
Author(s) -
Vaara Juha,
Ruud Kenneth,
Vahtras Olav
Publication year - 1999
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(199909)20:12<1314::aid-jcc12>3.0.co;2-0
Subject(s) - hamiltonian (control theory) , spin–orbit interaction , ab initio , dipole , physics , spin (aerodynamics) , perturbation theory (quantum mechanics) , ab initio quantum chemistry methods , fermi contact interaction , perturbation (astronomy) , condensed matter physics , atomic physics , quantum mechanics , electron , molecule , mathematical optimization , mathematics , thermodynamics
We present ab initio perturbation calculations of the electronic spin–orbit interaction contributions to indirect spin–spin coupling tensors using linear and quadratic response methods. The effects of both the Fermi‐contact and the spin–dipole interactions as well as the one‐ and two‐electron spin–orbit interactions are considered for the 1 J HX and 2 J HH couplings in the H 2 X (X=O, S, Se, and Te) and HX (X=F, Cl, Br, and I) systems using nonrelativistic multiconfiguration self‐consistent‐field reference states. Novel second‐order spin–orbit‐induced contributions to the J tensors due to the magnetic‐field dependence of the spin–orbit Hamiltonian are introduced and formulated as linear response functions. Calculations of these contributions are reported for the 2 J HH coupling tensors in the H 2 X systems. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1314–1327, 1999