Relativistic Effects on Electron–Nucleus Hyperfine Coupling Studied with an Exact 2-Component (X2C) Hamiltonian

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• 作者：Jochen Autschbach
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2017
• 出版时间：February 14, 2017
• 年：2017
• 卷：13
• 期：2
• 页码：710-718
• 全文大小：374K
• ISSN：1549-9626

文摘

An exact 2-component (X2C) transformation of the one-electron Hamiltonian is used to transform nuclear hyperfine magnetic field operators from the 4-component Dirac picture to 2-component form. Numerical applications are concerned with hyperfine coupling constants of one-electron and many-electron atoms, as well as the HgH radical, using spin-unrestricted scalar X2C Hartree–Fock and Kohn–Sham theory. Reference data for 2-component generalized-collinear X2C calculations, including spin–orbit coupling, are also provided for selected cases. Calculations for one-electron atomic n s states with n = 1–3 show that the X2C transformed hyperfine operators give accurate hyperfine coupling constants. Kohn–Sham one-electron self-interaction errors for these states are small. The performance of the X2C transformed hyperfine operator for many-electron systems is also promising. The method is straightforward to implement in codes using spin-unrestricted (1-component) or 2-component spinor orbitals.