环聚合物分子动力学：能量对称（接近热中性）插入反应（X + H₂）→ HX + H（X = C(¹D)，S(¹D)）的速率系数计算

Ring-polymer molecular dynamics: rate coefficient calculations for energetically symmetric (near thermoneutral) insertion reactions (X + H2) → HX + H(X = C(1D), S(1D)).

作者信息

Suleimanov Yury V, Kong Wendi J, Guo Hua, Green William H

机构信息

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

Department of Chemical and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.

出版信息

J Chem Phys. 2014 Dec 28;141(24):244103. doi: 10.1063/1.4904080.

DOI:10.1063/1.4904080

PMID:25554129

Abstract

Following our previous study of prototypical insertion reactions of energetically asymmetric type with the RPMD (Ring-Polymer Molecular Dynamics) method [Y. Li, Y. Suleimanov, and H. Guo, J. Phys. Chem. Lett. 5, 700 (2014)], we extend it to two other prototypical insertion reactions with much less exothermicity (near thermoneutral), namely, X + H2 → HX + H where X = C((1)D), S((1)D), in order to assess the accuracy of this method for calculating thermal rate coefficients for this class of reactions. For both chemical reactions, RPMD displays remarkable accuracy and agreement with the previous quantum dynamic results that make it encouraging for the future application of the RPMD to other barrier-less, complex-forming reactions involving polyatomic reactants with any exothermicity.

摘要

继我们之前使用环聚合物分子动力学（RPMD）方法对能量不对称型典型插入反应进行的研究[Y. Li、Y. Suleimanov和H. Guo，《物理化学快报》5，700（2014）]之后，我们将该方法扩展到另外两个放热少得多（接近热中性）的典型插入反应，即X + H₂ → HX + H，其中X = C((¹)D)、S((¹)D)，以评估该方法计算此类反应热速率系数的准确性。对于这两个化学反应，RPMD显示出了显著的准确性，并且与之前的量子动力学结果一致，这使得RPMD在未来应用于其他无势垒、涉及具有任何放热性的多原子反应物的复杂形成反应时令人鼓舞。