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

Journal Article · · Journal of Chemical Theory and Computation
 [1]
  1. University at Buffalo, State University of New York, NY (United States)
+ Show Author Affiliations
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. Furthermore, the method is straightforward to implement in codes using spin-unrestricted (1-component) or 2-component spinor orbitals.
Research Organization:
University at Buffalo, State University of New York, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001136
OSTI ID:
2479711
Alternate ID(s):
OSTI ID: 1534561
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 2 Vol. 13; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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