Issue 16, 2023

Improved modeling of anharmonicity for furan microsolvation

Abstract

Computational benchmark data for complexes requires accurate models of anharmonic torsional motion. State-of-the-art hindered rotor treatments come with a number of difficulties, regarding discontinuities from badly converged points or coupling, oscillations, or the consideration and correction of stationary points. Their manual handling introduces a level of arbitrariness not suitable for benchmark procedures. This study presents the TAMkinTools extension for improved modeling of one-dimensional hindered rotation which enables a more standardized workflow. We choose the structures from the Goebench challenge as test case, which comprises OH- and π-bonded complexes of methanol and furan, 2-methylfuran, and 2,5-dimethylfuran. Ahlrichs and Dunning basis sets of various sizes and their extrapolations show large differences in efficiency and accuracy for coupled-cluster energies of stationary points of these complexes. The probability density analysis of TAMkinTools provides zero-point energies for all conformations even within the same rotor profile. Zero-point energies show a large effect on the conformational order, especially for the methanol–furan complex with energy differences far below 1 kJ mol−1.

Graphical abstract: Improved modeling of anharmonicity for furan microsolvation

Supplementary files

Article information

Article type
Paper
Submitted
24 avg 2022
Accepted
27 mar 2023
First published
30 mar 2023

Phys. Chem. Chem. Phys., 2023,25, 11316-11323

Improved modeling of anharmonicity for furan microsolvation

W. A. Kopp, M. L. Mödden, N. Viswanathan, G. Rath and K. Leonhard, Phys. Chem. Chem. Phys., 2023, 25, 11316 DOI: 10.1039/D2CP03907A

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