Going beyond the routine consideration of solvent effects on 31P NMR shielding constants: a meticulous basis set study and new aug-pecS-n (n = 1, 2) basis sets for phosphorus atom

Abstract

In this paper, it was demonstrated that the accuracy of calculated solvent corrections to 31P NMR shielding constants of various phosphorus-containing molecules significantly depends on the basis set used. Highly positive role of diffuse functions was revealed not only for this issue, but also for phosphorus NMR shielding constants of anions. In light of this matter, the augmentation of the shift-oriented pecS-n (n = 1, 2) basis sets for phosphorus atom with diffuse functions was carried out using the property-energy consistent (PEC) method with the isotropic dipole polarizability used as main target property, being the first example of such way of augmentation of basis sets. Alongside with the other augmented basis sets of different types and quality, new aug-pecS-n (n = 1, 2) basis sets were shown to significantly improve the accuracy of the solvent corrections to 31P NMR shielding constants of neutral molecules and phosphorus shielding constants of anions as compared to their non-augmented analogies. Comparison with available experimental data corroborated theoretical findings.

Supplementary files

Article information

Article type
Paper
Submitted
23 Jan 2025
Accepted
26 Feb 2025
First published
27 Feb 2025

Phys. Chem. Chem. Phys., 2025, Accepted Manuscript

Going beyond the routine consideration of solvent effects on 31P NMR shielding constants: a meticulous basis set study and new aug-pecS-n (n = 1, 2) basis sets for phosphorus atom

Y. Yu. Rusakov, Y. A. Nikurashina and I. L. Rusakova, Phys. Chem. Chem. Phys., 2025, Accepted Manuscript , DOI: 10.1039/D5CP00313J

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