Chinese Physics B, Volume. 29, Issue 10, (2020)

Zero-point fluctuation of hydrogen bond in water dimer from ab initio molecular dynamics

Wan-Run Jiang1, Rui Wang1, Xue-Guang Ren2, Zhi-Yuan Zhang1, Dan-Hui Li1, and Zhi-Gang Wang1、†
Author Affiliations
  • 1Institute of Atomic and Molecular Physics, Jilin University, Changchun 3002, China
  • 2School of Science, Xi’an Jiaotong University, Xi’an 710049, China
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    Dynamic nature of hydrogen bond (H-bond) is central in molecular science of substance transportation, energy transfer, and phase transition in H-bonding networks diversely expressed as solution, crystal, and interfacial systems, thus attracting the state-of-the-art revealing of its phenomenological edges and sophisticated causes. However, the current understanding of the ground-state fluctuation from zero-point vibration (ZPV) lacks a firm quasi-classical base, concerning three basic dimensions as geometry, electronic structure, and interaction energy. Here, based on the ab initio molecular dynamics simulation of a ground-state water dimer, temporally separated fluctuation features in the elementary H-bond as the long-time weakening and the minor short-time strengthening are respectively assigned to two low-frequency intermolecular ZPV modes and two O–H stretching ones. Geometrically, the former modes instantaneously lengthen H-bond up to 0.2 ? whose time-averaged effect coverages to about 0.03 ? over 1-picosecond. Electronic-structure fluctuation crosses criteria’ borders, dividing into partially covalent and noncovalent H-bonding established for equilibrium models, with a 370% amplitude and the district trend in interaction energy fluctuation compared with conventional dragging models using frozen monomers. Extended physical picture within the normal-mode disclosure further approaches to the dynamic nature of H-bond and better supports the upper-building explorations towards ultrafast and mode-specific manipulation.

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    Wan-Run Jiang, Rui Wang, Xue-Guang Ren, Zhi-Yuan Zhang, Dan-Hui Li, Zhi-Gang Wang. Zero-point fluctuation of hydrogen bond in water dimer from ab initio molecular dynamics[J]. Chinese Physics B, 2020, 29(10):

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    Paper Information

    Received: Mar. 23, 2020

    Accepted: --

    Published Online: Apr. 21, 2021

    The Author Email: Wang Zhi-Gang (wangzg@jlu.edu.cn)

    DOI:10.1088/1674-1056/abab6d

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