期刊
JOURNAL OF CHEMICAL PHYSICS
卷 133, 期 6, 页码 -出版社
AIP Publishing
DOI: 10.1063/1.3466767
关键词
ab initio calculations; association; free energy; molecular dynamics method; organometallic compounds; perturbation theory; photochemistry; reaction kinetics theory; thermochemistry
资金
- French CINES [lct2550]
- IDRIS [lct2550]
We describe an efficient and accurate method to compute free energy changes in complex chemical systems that cannot be described through classical molecular dynamics simulations, examples of which are chemical and photochemical reactions in solution, enzymes, interfaces, etc. It is based on the use of dual-level Born-Oppenheimer molecular dynamics simulations. A low-level quantum mechanical method is employed to calculate the potential of mean force through the umbrella sampling technique. Then, a high-level quantum mechanical method is used to estimate a free energy correction on selected points of the reaction coordinate using perturbation theory. The precision of the results is comparable to that of ab initio molecular dynamics methods such as the Car-Parrinello approach but the computational cost is much lower, roughly by two to three orders of magnitude. The method is illustrated by discussing the association free energy of simple organometallic compounds, although the field of application is very broad. (C) 2010 American Institute of Physics. [doi:10.1063/1.3466767]
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据