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

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

doi:10.1063/1.4904080

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

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

Authors

Yury V Suleimanov¹, Wendi J Kong¹, Hua Guo², William H Green¹

Affiliations

¹ Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
² Department of Chemical and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.

PMID: 25554129
DOI: 10.1063/1.4904080

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.