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Weijo V, Bast R, Manninen P, et al. Methodological aspects in the calculation of parity-violating effects in nuclear magnetic resonance parameters. J Chem Phys. 2007;126(7):074107doi: 10.1063/1.2436886.
Weijo, V., Bast, R., Manninen, P., Saue, T., & Vaara, J. (2007). Methodological aspects in the calculation of parity-violating effects in nuclear magnetic resonance parameters. The Journal of chemical physics, 126(7), 074107. https://doi.org/10.1063/1.2436886
Weijo, Ville, et al. "Methodological aspects in the calculation of parity-violating effects in nuclear magnetic resonance parameters." The Journal of chemical physics vol. 126,7 (2007): 074107. doi: https://doi.org/10.1063/1.2436886
Weijo V, Bast R, Manninen P, Saue T, Vaara J. Methodological aspects in the calculation of parity-violating effects in nuclear magnetic resonance parameters. J Chem Phys. 2007 Feb 21;126(7):074107. doi: 10.1063/1.2436886. PMID: 17328593.
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J Chem Phys. 2007 Feb 21;126(7):074107. doi: 10.1063/1.2436886.

Methodological aspects in the calculation of parity-violating effects in nuclear magnetic resonance parameters.

The Journal of chemical physics

Ville Weijo, Radovan Bast, Pekka Manninen, Trond Saue, Juha Vaara

Affiliations

  1. Laboratory of Physical Chemistry, Department of Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), University of Helsinki, FI-00014, Helsinki, Finland.

PMID: 17328593 DOI: 10.1063/1.2436886

Abstract

We examine the quantum chemical calculation of parity-violating (PV) electroweak contributions to the spectral parameters of nuclear magnetic resonance (NMR) from a methodological point of view. Nuclear magnetic shielding and indirect spin-spin coupling constants are considered and evaluated for three chiral molecules, H2O2, H2S2, and H2Se2. The effects of the choice of a one-particle basis set and the treatment of electron correlation, as well as the effects of special relativity, are studied. All of them are found to be relevant. The basis-set dependence is very pronounced, especially at the electron correlated ab initio levels of theory. Coupled-cluster and density-functional theory (DFT) results for PV contributions differ significantly from the Hartree-Fock data. DFT overestimates the PV effects, particularly with nonhybrid exchange-correlation functionals. Beginning from third-row elements, special relativity is of importance for the PV NMR properties, shown here by comparing perturbational one-component and various four-component calculations. In contrast to what is found for nuclear magnetic shielding, the choice of the model for nuclear charge distribution--point charge or extended (Gaussian)--has a significant impact on the PV contribution to the spin-spin coupling constants.

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