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Describing nuclear quantum effects in vibrational properties using molecular dynamics with Wigner sampling†
Denis S. Tikhonov,Yury V. Vishnevskiy
Physical Chemistry Chemical Physics Pub Date : 06/20/2023 00:00:00 , DOI:10.1039/D3CP01007D
Abstract

In this work we discuss the generally applicable Wigner sampling and introduce a new, simplified Wigner sampling method, for computationally effective modeling of molecular properties containing nuclear quantum effects and vibrational anharmonicity. For various molecular systems test calculations of (a) vibrationally averaged rotational constants, (b) vibrational IR spectra and (c) photoelectron spectra have been performed. The performance of Wigner sampling has been assessed by comparing with experimental data and with results of other theoretical models, including harmonic and VPT2 approximations. The developed simplified Wigner sampling method shows advantages in application to large and flexible molecules.

Graphical abstract: Describing nuclear quantum effects in vibrational properties using molecular dynamics with Wigner sampling
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