Atomic isotropic hyperfine properties for first row elements (B–F) revisited

Feller, David; Stanton, John F.; Davidson, Ernest R.

doi:10.1063/5.0080155

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Atomic isotropic hyperfine properties for first row elements (B–F) revisited

Feller, David·Stanton, John F.·Davidson, Ernest R.

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Abstract

Benchmark quality isotropic hyperfine properties have been obtained for first row elements (B–F) using a systematic composite approach consisting of a sequence of core/valence correlation consistent basis sets, up through aug-cc-pCV8Z, along with configuration interaction and coupled cluster theory methods. The best nonrelativistic final values (in MHz) are 10.64 (B), 20.22 (C), 10.59 (N), –31.74 (O), and 318.30 (F) and are in very good agreement with available experimental values for these difficult-to-describe properties. Agreement is especially close in the case of N, which has the most accurate experimental value. The spin densities derived from the best composite level of theory were found to closely follow a simple quadratic scaling with the atomic number, Z. Finally, observed convergence rates in the 1-particle and n-particle expansions obtained here may be useful in judging likely accuracy that can be expected in studies of molecular systems.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS Configuration interaction Correlation-consistent basis sets Coupled-cluster methods Density functional theory Electron paramagnetic resonance spectroscopy Hyperfine structure Multi-configurational self-consistent field Restricted open-shell Hartree-Fock Unrestricted Hartree-Fock

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Feller, David, Stanton, John F., Davidson, Ernest R.. 2022-01-19. Atomic isotropic hyperfine properties for first row elements (B–F) revisited. https://doi.org/10.1063/5.0080155

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