物理化学学报 >> 2013, Vol. 29 >> Issue (10): 2173-2179.doi: 10.3866/PKU.WHXB201308272

理论与计算化学 上一篇    下一篇

水团簇构象稳定性起源和本质的密度泛函理论与量子分子动力学研究

王友娟1, 赵东波1, 荣春英1, 刘述斌1,2   

  1. 1 湖南师范大学化学化工学院, 资源精细化与先进材料湖南省高校重点实验室, 化学生物学及中药分析教育部重点实验室, 长沙 410081;
    2 Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, U.S.A.
  • 收稿日期:2013-06-27 修回日期:2013-08-27 发布日期:2013-09-26
  • 通讯作者: 荣春英, 刘述斌 E-mail:rongchunying@aliyun.com;shubin@email.unc.edu
  • 基金资助:

    湖南师范大学“潇湘学者”杰出人才项目(23040609);湖南省研究生创新项目(CX2012B223)以及湖南省高等教育机构科技创新研究团队项目资助

Towards Understanding the Origin and Nature of the Conformational Stability of Water Clusters:a Density Functional Theory and Quantum Molecular Dynamics Study

WANG You-Juan1, ZHAO Dong-Bo1, RONG Chun-Ying1, LIU Shu-Bin1,2   

  1. 1 Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, P. R. China;
    2 Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, U.S.A.
  • Received:2013-06-27 Revised:2013-08-27 Published:2013-09-26
  • Contact: RONG Chun-Ying, LIU Shu-Bin E-mail:rongchunying@aliyun.com;shubin@email.unc.edu
  • Supported by:

    The project was supported by the‘XiaoXiang Scholar’Talents Foundation of Hunan Normal University, China (23040609), Hunan Provincial Innovation Foundation for Postgraduate, China (CX2012B223), and Aid Programfor Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province, China.

摘要:

寻找确定分子体系构象稳定性的关键因素是至关重要的, 但即使对最简单的分子, 其稳定性的起源和本质仍存在很大的争议. 本文以水团簇为例, 采用量子分子动力学产生185个八聚水分子团簇模型, 并运用基于密度泛函理论的两个能量分解方法寻找其稳定性的决定因素. 我们发现不同水团簇的稳定性与其立体排斥能和交换相关能成良好的线性关系.本文还采用双变量模型模拟水团簇的稳定性, 取得了更好的结果(相关系数大于0.99). 本工作对揭示包括水分子团簇在内的通过弱相互作用组成的分子络合物的稳定性起源和本质提供了有益启示.

关键词: 水分子团簇, 量子分子动力学, 密度泛函理论, 立体效应, 交换相关能

Abstract:

To find out what interaction dictates the molecular stability is essential, yet still controversial even for simplest molecules. Here, using water cluster as an example, we employ quantum molecular dynamics to generate a total of 185 conformations for octamer water clusters and then employ two energy partition schemes from density functional theory to pinpoint the principles governing their stability. We found that their stability is strongly correlated with steric repulsion and exchange-correlation interactions. Explanations using two different quantities are also proposed (with the correlation coefficient larger than 0.99). This work sheds light to the fundamental understanding towards the origin and nature of molecular conformational stability for water clusters and other molecular complexes formed through intermolecular interactions.

Key words: Water cluster, Quantum molecular dynamics, Density functional theory, Steric effect, Exchange-correlation energy

MSC2000: 

  • O641