arXivDaily arXiv每日学术速递 周一至周五更新
arXiv周末暂无论文更新,休息一下吧,周末愉快~~
arXiv 0909.5381cond-mat.mes-hallcond-mat.softphysics.chem-phq-bio.BM
收藏

稀有热活化反应的从头算动力学

Ab-initio Dynamics of Rare Thermally Activated Reactions

S. a Beccara, G. Garberoglio, P. Faccioli, F. Pederiva

摘要:

我们引入了一个框架来从头计算研究稀有热活化反应的动力学。电子的自由度在量子力学水平的玻恩-奥本海默近似下描述,而核的自由度通过朗之万方程耦合到热浴。该方法是基于路径积分表示的随机动力学和产量的时间演化的核和电子的自由度,沿最可能的反应途径,而不花费计算时间来探索亚稳态。这种方法是非常有效的,并允许研究热活化反应,不能使用从头计算分子动力学技术模拟。作为第一个说明性的应用程序,我们的特点在环丁烯丁二烯反应的主导途径。

英文摘要:

We introduce a framework to investigate ab-initio the dynamics of rare thermally activated reactions. The electronic degrees of freedom are described at the quantum-mechanical level in the Born-Oppenheimer approximation, while the nuclear degrees of freedom are coupled to a thermal bath, through a Langevin equation. This method is based on the path integral representation for the stochastic dynamics and yields the time evolution of both nuclear and electronic degrees of freedom, along the most probable reaction pathways, without spending computational time to explore metastable states. This approach is very efficient and allows to study thermally activated reactions which cannot be simulated using ab-initio molecular dynamics techniques. As a first illustrative application, we characterize the dominant pathway in the cyclobutene to butadiene reaction.

机构、总结、中文摘要均由AI分析而来,可能存在错误,请以论文正文为准。

↑