Path integral Brownian chain molecular dynamics : A simple approximation of quantum vibrational dynamics
© 2022 Wiley Periodicals LLC.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 43(2022), 27 vom: 15. Okt., Seite 1864-1879 |
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| 1. Verfasser: | |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2022
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article ab initio simulations molecular dynamics path integral simulations semiclassical theory vibrational dynamics |
| Zusammenfassung: | © 2022 Wiley Periodicals LLC. An approximate approach to quantum vibrational dynamics, "Brownian chain molecular dynamics (BCMD)," is proposed to alleviate the chain resonance and curvature problems in the imaginary time-based path integral (PI) simulation. Here the non-centroid velocity is randomized at each step when solving the equation of motion of path integral molecular dynamics. This leads to a combination of the Newton equation and the overdamped Langevin equation for the centroid and non-centroid variables, respectively. BCMD shares the basic properties of other PI approaches such as centroid and ring polymer molecular dynamics: It gives the correct Kubo-transformed correlation function at short times, conserves the time symmetry, has the correct high-temperature/classical limits, gives exactly the position and velocity autocorrelations of harmonic oscillator systems, and does not have the zero-point leakage problem. Numerical tests were done on simple molecular models and liquid water. On-the-fly ab initio BCMD simulations were performed for the protonated water cluster, H 5 O 2 + , and its isotopologue, D 5 O 2 + |
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| Beschreibung: | Date Revised 19.09.2022 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.26989 |