VTST and RPMD kinetics study of the nine-body X + C2 H6 (X ≡ H, Cl, F) reactions based on analytical potential energy surfaces

Physical Chemistry Chemical Physics : PCCP
Joaquin Espinosa-GarciaYury V Suleimanov

Abstract

Thermal rate constants of nine-atom hydrogen abstraction reactions, X + C2H6 → HX + C2H5 (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 + C2H6 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(2P) 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 temperatu...Continue Reading

References

Feb 9, 1987·Physical Review Letters·M J Gillan
Aug 12, 2004·The Journal of Chemical Physics·Ian R Craig, David E Manolopoulos
May 12, 2009·The Journal of Chemical Physics·Rosana Collepardo-GuevaraDavid E Manolopoulos
Dec 9, 2009·The Journal of Chemical Physics·Jeremy O Richardson, Stuart C Althorpe
Feb 2, 2011·The Journal of Chemical Physics·Yury V SuleimanovDavid E Manolopoulos
Feb 7, 2013·Physical Chemistry Chemical Physics : PCCP·Yury V SuleimanovF Javier Aoiz
Jan 5, 2014·The Journal of Physical Chemistry. a·J Espinosa-GarciaJ C Corchado
Jan 16, 2014·Physical Chemistry Chemical Physics : PCCP·R Pérez de TudelaF J Aoiz
Apr 9, 2015·The Journal of Physical Chemistry. B·Yury V Suleimanov, J Espinosa-Garcia
Aug 19, 2015·The Journal of Physical Chemistry Letters·Ricardo Pérez de TudelaF J Aoiz
Feb 16, 2012·The Journal of Physical Chemistry Letters·Ricardo Pérez de TudelaDavid E Manolopoulos
Jan 12, 2010·Journal of Chemical Theory and Computation·Rubén Meana-PañedaAntonio Fernández-Ramos
Nov 4, 2016·The Journal of Physical Chemistry. a·Yury V SuleimanovHua Guo
Dec 3, 2016·Physical Chemistry Chemical Physics : PCCP·Kevin M Hickson, Yury V Suleimanov
Feb 17, 2017·The Journal of Physical Chemistry. a·Kevin M Hickson, Yury V Suleimanov
Jul 14, 2017·Physical Chemistry Chemical Physics : PCCP·Joaquin Espinosa-GarciaYury V Suleimanov
Jul 25, 2018·Physical Chemistry Chemical Physics : PCCP·J Espinosa-GarciaC Rangel
Dec 14, 2018·Physical Chemistry Chemical Physics : PCCP·Dóra PappGábor Czakó
Aug 30, 2019·The Journal of Physical Chemistry. a·Dianailys Nuñez-ReyesYury V Suleimanov
May 23, 2020·The Journal of Physical Chemistry Letters·Dóra PappGábor Czakó

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Citations

Oct 2, 2020·Physical Chemistry Chemical Physics : PCCP·J Espinosa-GarciaM Garcia-Chamorro
Nov 12, 2021·Physical Chemistry Chemical Physics : PCCP·Kevin M HicksonDaniela V Coelho
Nov 27, 2021·Physical Chemistry Chemical Physics : PCCP·Delu Gao, Dunyou Wang

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Software Mentioned

RPMDrate
RPMD
POLYRATE
VTST
MT

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