...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Physical Review X >Ultrafast Vibrational Dynamics of Water Disentangled by Reverse Nonequilibrium Ab?Initio Molecular Dynamics Simulations
【24h】

Ultrafast Vibrational Dynamics of Water Disentangled by Reverse Nonequilibrium Ab?Initio Molecular Dynamics Simulations

机译：反向非平衡从头算分子动力学模拟解开水的超快振动动力学

获取原文
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Water is a unique solvent with strong, yet highly dynamic, intermolecular interactions. Many insights into this distinctive liquid have been obtained using ultrafast vibrational spectroscopy of water’s O-H stretch vibration. However, it has been challenging to separate the different contributions to the dynamics of the O-H stretch vibration in H2O. Here, we present a novel nonequilibrium molecular dynamics (NEMD) algorithm that allows for a detailed picture of water vibrational dynamics by generating nonequilibrium vibrationally excited states at targeted vibrational frequencies. Our ab?initio NEMD simulations reproduce the experimentally observed time scales of vibrational dynamics in H2O. The approach presented in this work uniquely disentangles the effects on the vibrational dynamics of four contributions: the delocalization of the O-H stretch mode, structural dynamics of the hydrogen bonded network, intramolecular coupling within water molecules, and intermolecular coupling between water molecules (near-resonant energy transfer between O-H groups). Our results illustrate that intermolecular energy transfer and the delocalization of the O-H stretch mode are particularly important for the spectral diffusion in H2O.Received 22 July 2014DOI:This article is available under the terms of the Creative Commons Attribution 3.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.Published by the American Physical Society
机译：水是一种独特的溶剂，具有强而动态的分子间相互作用。使用水的O-H拉伸振动的超快振动光谱学，已经获得了对该独特液体的许多见解。但是，将对H2O中O-H拉伸振动动力学的不同影响分开是有挑战性的。在这里，我们提出了一种新颖的非平衡分子动力学（NEMD）算法，该算法通过在目标振动频率处生成非平衡振动激发态来详细了解水的振动动力学。我们从头开始的NEMD模拟再现了实验观察到的H2O振动动力学的时间尺度。这项工作中提出的方法独特地消除了对四个贡献的振动动力学的影响：OH拉伸模式的离域，氢键网络的结构动力学，水分子内的分子内偶联以及水分子之间的分子间偶联（近共振） OH基团之间的能量转移）。我们的结果表明，分子间的能量转移和O-H拉伸模式的离域对于H2O中的光谱扩散尤为重要.2014年7月22日接收DOI：本文可根据知识共享署名3.0许可的条款获得。此作品的进一步分发必须保持作者的姓名和所发表文章的标题，期刊引文以及DOI的归属。美国物理学会出版

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号