VTST and RPMD kinetics study of the nine-body X + C2H6 (X ≡ H, Cl, F) reactions based on analytical potential energy surfaces. Issue 24 (15th June 2020)

• Record Type: Journal Article
• Authors: Espinosa-Garcia, Joaquin; Garcia-Chamorro, Moises; Corchado, Jose C.; Bhowmick, Somnath; Suleimanov, Yury V.
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 24(2020)
• Page Start: 13790
• Page End: 13801
• Publication Date: 2020-06-15
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d0cp02238a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The X + C2 H6 (X ≡ H, Cl, F) reaction rate constant has been calculated within a wide temperature range (189–2000 K) using variational transition state theory with multidimensional tunnelling and ring polymer molecular dynamics methods. Abstract : Thermal rate constants of nine-atom hydrogen abstraction reactions, X + C2 H6 → HX + C2 H5 (X ≡ H, Cl, F) with qualitatively different reaction paths, have been investigated using two kinetics approaches – variational transition state theory with multidimensional tunnelling (VTST/MT) and ring polymer molecular dynamics (RPMD) – and full dimensional analytical potential energy surfaces. For the H + C2 H6 reaction, which proceeds through a noticeable barrier height of 11.62 kcal mol −1, kinetics approaches showed excellent agreement between them (with differences less than 30%) and with the experiment (with differences less than 60%) in the wide temperature range of 200–2000 K. For X = Cl and F, however, the situation is very different. The barrier height is either low or very low, 2.44 and 0.23 kcal mol −1, respectively, and the presence of van der Waals complexes in the entrance channel leads to a very flat topography and, consequently, imposes theoretical challenges. For the Cl( 2 P) reaction, VTST/MT underestimates the experimental rate constants (with differences less than 86%), and RPMD demonstrates better agreement (with differences less than 47%), although the temperature dependence is opposite to the experiment at low temperatures. Finally, for the F( 2 P) reaction, available experimental information shows discrepancies, both in the absolute values of the rate constants and also in the temperature dependence. Unfortunately, kinetics theories did not resolve this discrepancy. Different possible causes of these theory/experiment discrepancies were analyzed.