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DOE OSTI · 1831062

Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Feng, Rulin·Duignan, Thomas J.·Autschbach, Jochen
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Abstract

Exact two-component (X2C) relativistic nuclear hyperfine magnetic field operators were incorporated in X2C ab-initio wavefunction calculations at the multi-reference restricted active space (RAS) level for calculations of nuclear hyperfine magnetic properties. Spin-orbit coupling was treated via RAS state interaction (SO-RASSI). The method was tested by calculations of electron – nucleus hyperfine coupling constants. The approach, implemented in the OpenMolcas program, overcomes a major limitation of a previous SO-RASSI implementation for hyperfine coupling that relied on non-relativistic hyperfine operators [J. Chem. Theor. Comput. 2015, 11, 538–549] and therefore had only limited applicability. Furthermore, results from calculations on systems with light and heavy main group elements, transition metals, lanthanides, and one actinide complex, demonstrate reasonably good agreement with experimental data, where available, as long as the active space can generate sufficient spin polarization.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYChemical calculationsMagnetic propertiesMathematical methodsOrganic compoundsQuantum mechanics

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Feng, Rulin, Duignan, Thomas J., Autschbach, Jochen. 2021-01-01. Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian. https://doi.org/10.1021/acs.jctc.0c01005

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