Relativistic theory of nuclear spin-rotation tensor with kinetically balanced rotational London orbitals

Yunlong Xiao; Yong Zhang; Wenjian Liu

doi:10.1063/1.4898631

Relativistic theory of nuclear spin-rotation tensor with kinetically balanced rotational London orbitals

J Chem Phys. 2014 Oct 28;141(16):164110. doi: 10.1063/1.4898631.

Authors

Yunlong Xiao¹, Yong Zhang¹, Wenjian Liu¹

Affiliation

¹ Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, and Center for Computational Science and Engineering, Peking University, Beijing 100871, People's Republic of China.

PMID: 25362275
DOI: 10.1063/1.4898631

Abstract

Both kinetically balanced (KB) and kinetically unbalanced (KU) rotational London orbitals (RLO) are proposed to resolve the slow basis set convergence in relativistic calculations of nuclear spin-rotation (NSR) coupling tensors of molecules containing heavy elements [Y. Xiao and W. Liu, J. Chem. Phys. 138, 134104 (2013)]. While they perform rather similarly, the KB-RLO Ansatz is clearly preferred as it ensures the correct nonrelativistic limit even with a finite basis. Moreover, it gives rise to the same "direct relativistic mapping" between nuclear magnetic resonance shielding and NSR coupling tensors as that without using the London orbitals [Y. Xiao, Y. Zhang, and W. Liu, J. Chem. Theory Comput. 10, 600 (2014)].