Relativistic Theory of Nuclear Spin-Rotation Tensor
The relativistic theory for the nuclear spin-rotation (NSR) tensor is formulated based on the body-fixed molecular Hamiltonian that treats quantum electrons fully relativistically and quantum nuclei quasi-relativistically. The resulting expression for the NSR tensor is then compared with that for the nuclear magnetic shielding tensor, so as to establish a relativistic mapping between them. This relativistic mapping is very robust and permits an easy and direct translation of experimental NSR tensors into semi-experimental absolute nuclear shielding tensors which are otherwise difficult to obtain experimentally. In contrast, the well-known nonrelativistic mapping (Ramsey–Flygare relation) between the nuclear shielding and NSR tensors breaks down even for relatively light elements. Some classic systems are taken as examples to elucidate the concepts.
KeywordsRelativistic molecular Hamiltonian Nuclear spin-rotation Nuclear magnetic resonance Relativistic mapping Rotational London orbitals
The research of this work was supported by grants from the NSFC (Project Nos. 21033001, 21273011, 21473002, 21173006, and 21290192). KR acknowledges support from the Research Council of Norway through a Centre of Excellence Grant (Grant No. 179568) and helpful discussions with S. Komorovský.
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