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

14 June 2023, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


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 have been performed test calculations of (a) vibrationally averaged rotational constants, (b) vibrational IR spectra and (c) photoelectron spectra. 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.


molecular dynamics
Wigner sampling
molecular vibrations

Supplementary materials

Supporting information
Contains computational details of simulations


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