Mode-specific multi-channel dynamics of the F- + CHD2Cl reaction on a global ab initio potential energy surface

István Szabó, G. Czakó

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

We report a detailed quasiclassical trajectory study for the dynamics of the ground-state and CH/CD stretching-excited F- + CHD2Cl(vCH/CD = 0, 1) → Cl- + CHD2F, HF + CD2Cl-, and DF + CHDCl- SN2, proton-, and deuteron-abstraction reactions using a full-dimensional global ab initio analytical potential energy surface. The simulations show that (a) CHD2Cl(vCH/CD = 1), especially for vCH = 1, maintains its mode-specific excited character prior to interaction, (b) the SN2 reaction is vibrationally mode-specific, (c) double inversion can occur and is enhanced upon CH/CD stretching excitations, (d) in the abstraction reactions the HF channel is preferred and the vCH/CD = 1 excitations significantly promote the HF/DF channels, (e) back-side rebound, back-side stripping, and front-side stripping are the dominant direct abstraction mechanisms based on correlated scattering- and attack-angle distributions, (f) the exact classical vibrational energy-based Gaussian binning (1GB) provides realistic mode-specific polyatomic product state distributions, (g) in the abstraction reactions CH and CD stretchings are not pure spectator modes and mainly ground-state products are produced, thus most of the initial energy transfers into product translation, and (h) the HF and DF product molecules are rotationally cold without any significant dependence on the reactant's and HF/DF vibrational states.

Original languageEnglish
Article number134303
JournalJournal of Chemical Physics
Volume145
Issue number13
DOIs
Publication statusPublished - Oct 7 2016

Fingerprint

Potential energy surfaces
deuterium fluorides
Stretching
potential energy
Ground state
methylidyne
products
stripping
Deuterium
Energy transfer
ground state
Protons
Trajectories
vibrational states
Scattering
attack
excitation
deuterons
Molecules
energy transfer

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Mode-specific multi-channel dynamics of the F- + CHD2Cl reaction on a global ab initio potential energy surface. / Szabó, István; Czakó, G.

In: Journal of Chemical Physics, Vol. 145, No. 13, 134303, 07.10.2016.

Research output: Contribution to journalArticle

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