Issue 3, 2023

Benchmarking the quadrupolar coupling tensor for chlorine to probe weak-bonding interactions

Abstract

Rotational spectroscopy relies on quantum chemical calculations to interpret observed spectra. Among the most challenging molecules to assign are those with additional angular momenta coupling to the rotation, contributing to the complexity of the spectrum. This benchmark study of computational methods commonly used by rotational spectroscopists targets the nuclear quadrupole coupling constants of chlorine containing molecules and the geometry of its complexes and clusters. For each method, the quality of both structural and electronic parameter predictions is compared with the experimental values. Ab initio methods are found to perform best overall in predicting both the geometry of the complexes and the coupling constants of chlorine with moderate computational cost. This cost can be reduced by combining these methods with density functional theory structure optimization, which still yields adequate predictions. This work constitutes a first step in expanding Bailey's quadrupole coupling data set to encompass molecular clusters. [W. C. Bailey, Calculation of Nuclear Quadrupole Coupling Constants in Gaseous State Molecule, 2019, https://nqcc.wcbailey.net/]

Graphical abstract: Benchmarking the quadrupolar coupling tensor for chlorine to probe weak-bonding interactions

Supplementary files

Article information

Article type
Paper
Submitted
01 Sep 2022
Accepted
13 Dec 2022
First published
14 Dec 2022
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2023,25, 2420-2429

Benchmarking the quadrupolar coupling tensor for chlorine to probe weak-bonding interactions

R. Dohmen, D. Fedosov and D. A. Obenchain, Phys. Chem. Chem. Phys., 2023, 25, 2420 DOI: 10.1039/D2CP04067K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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