Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany.
2Lehrstuhl für Anorganische Chemie und Strukturchemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, 33615 Bielefeld, Germany.
Phys Chem Chem Phys. 2023 Jul 12;25(27):18406-18423. doi: 10.1039/d3cp01007d.
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.
在这项工作中，我们讨论了普遍适用的维格纳采样，并引入了一种新的、简化的维格纳采样方法，用于计算有效地建模包含核量子效应和振动非谐性的分子性质。对于各种分子系统，已经进行了（a）振动平均旋转常数、（b）振动红外光谱和（c）光电子能谱的测试计算。通过与实验数据和其他理论模型（包括谐波和 VPT2 近似）的结果进行比较，评估了维格纳采样的性能。所开发的简化维格纳采样方法在应用于大型和灵活的分子方面具有优势。
