Metadynamics with Discriminants: A Tool for Understanding Chemistry,Journal of Chemical Theory and Computation

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Metadynamics with Discriminants: A Tool for Understanding Chemistry
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-09-17 00:00:00 , DOI: 10.1021/acs.jctc.8b00634
GiovanniMaria Piccini _{1,

2} , Dan Mendels _{1,

2} , Michele Parrinello _{1,

2}

Affiliation

We introduce an extension of a recently published method [Mendels et al. J. Phys. Chem. Lett. 2018, 9, 2776−2781] to obtain low-dimensional collective variables for studying multiple states free energy processes in chemical reactions. The only information needed is a collection of simple statistics of the equilibrium properties of the reactants and product states. No information on the reaction mechanism has to be given. The method allows studying a large variety of chemical reactivity problems including multiple reaction pathways, isomerization, and stereo- and regiospecificity. We applied the method to two fundamental organic chemical reactions. First we study the S_N2 nucleophilic substitution reaction of a Cl in CH₂Cl₂ leading to an understanding of the kinetic origin of the chirality inversion in such processes. Subsequently, we tackle the problem of regioselectivity in the hydrobromination of propene revealing that the nature of empirical observations such as Markovnikov’s rule lies in the chemical kinetics rather than the thermodynamic stability of the products.

中文翻译：

带有判别式的元动力学：了解化学的工具

我们介绍了最近发布的方法的扩展[Mendels等。J.物理化学来吧 2018，9，2776年至2781年]，得到低维集体变量，以在化学反应研究多个状态自由能的过程。唯一需要的信息是反应物和产物状态的平衡特性的简单统计数据的集合。无需提供有关反应机理的任何信息。该方法可以研究各种各样的化学反应性问题，包括多个反应途径，异构化以及立体和区域特异性。我们将该方法应用于两个基本的有机化学反应。首先我们研究了CH ₂ Cl中Cl的S _N 2亲核取代反应₂导致对这种过程中手性反转的动力学起源的理解。随后，我们解决了丙烯加氢溴化反应中区域选择性的问题，从而揭示了诸如马尔科夫尼科夫定律这样的经验观察的本质在于产品的化学动力学而非热力学稳定性。

更新日期：2018-09-17

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