Theoretical study of the nuclear spin-molecular rotation coupling for relativistic electrons and non-relativistic nuclei

• Autores: Aucar, I.A.; Gómez, S.S.; De Azúa, M.C.R.; Giribet, C.G.
• Año de publicación: 2012
• Idioma: inglés
• Tipo de recurso: artículo
• Fuente: J Chem Phys 2012;136(20)
• Materia: Born-Oppenheimer; Linear response; Molecular Hamiltonian; Molecular rotations; Nuclear magnetic shieldings; Perturbative expansion; Relativistic effects; Relativistic electron; Small components; Spectral parameters; Spin-rotations; Theoretical expression; Theoretical study; Magnetic shielding; Molecular dynamics; Stereochemistry; Tensors
• Institución: Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturales

A theoretical study of the relation between the relativistic formulation of the nuclear magnetic shielding and spin-rotation tensors is presented. To this end a theoretical expression of the relativistic spin-rotation tensor is formulated, considering a molecular Hamiltonian of relativistic electrons and non-relativistic nuclei. Molecular rotation effects are introduced considering the terms of the Born-Oppenheimer decomposition, which couple the electrons and nuclei dynamics. The loss of the simple relation linking both spectral parameters in the non-relativistic formulation is further analyzed carrying out a perturbative expansion of relativistic effects by means of the linear response within the elimination of the small component approach. It is concluded that relativistic effects on the spin-rotation tensor are less important than those of the nuclear magnetic shielding tensor. © 2012 American Institute of Physics.
Fil:Giribet, C.G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.