Four-Component Relativistic Density-Functional Theory Calculations of Nuclear Spin鈥揜otation Constants: Relativistic Effects in p-Block Hydrides

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• 作者：Stanislav Komorovsky ; Michal Repisky ; Elena Malkin ; Taye B. Demissie ; Kenneth Ruud
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2015
• 出版时间：August 11, 2015
• 年：2015
• 卷：11
• 期：8
• 页码：3729-3739
• 全文大小：439K
• ISSN：1549-9626

文摘

We present an implementation of the nuclear spin鈥搑otation (SR) constants based on the relativistic four-component Dirac鈥揅oulomb Hamiltonian. This formalism has been implemented in the framework of the Hartree鈥揊ock and Kohn鈥揝ham theory, allowing assessment of both pure and hybrid exchange鈥揷orrelation functionals. In the density-functional theory (DFT) implementation of the response equations, a noncollinear generalized gradient approximation (GGA) has been used. The present approach enforces a restricted kinetic balance condition for the small-component basis at the integral level, leading to very efficient calculations of the property. We apply the methodology to study relativistic effects on the spin鈥搑otation constants by performing calculations on XH<sub>nsub> (n = 1鈥?) for all elements X in the p-block of the periodic table and comparing the effects of relativity on the nuclear SR tensors to that observed for the nuclear magnetic shielding tensors. Correlation effects as described by the density-functional theory are shown to be significant for the spin鈥搑otation constants, whereas the differences between the use of GGA and hybrid density functionals are much smaller. Our calculated relativistic spin鈥搑otation constants at the DFT level of theory are only in fair agreement with available experimental data. It is shown that the scaling of the relativistic effects for the spin鈥搑otation constants (varying between Z<sup>3.8sup> and Z<sup>4.5sup>) is as strong as for the chemical shieldings but with a much smaller prefactor.