State-to-state chemistry with fast hydrogen atoms

Reaction and collisional excitation in H + CO2

George C Schatz, Michael S. Fitzcharles, Lawrence B. Harding

Research output: Contribution to journalArticle

179 Citations (Scopus)

Abstract

We present a detailed theoretical study of vibrational-rotational excitation and reaction in collisions of CO2 with 1.9-2.6 eV hydrogen atoms. Minima and saddle points on the potential surface have been characterized using ab initio configuration interaction calculations, and a global surface has been developed by a combination of many-body expansion and surface-fitting methods. The collision dynamics have been studied using quasiclassical trajectories, with the CO2 vibrational states characterized by a Fourier-transform action calculation. For non-reactive scattering there is reasonable correlation between the vibrational modes that are excited and the regions of the potential surface sampled during the collisions. Most of the lower states of CO2 are excited by direct collisions that do not sample potential wells. Collisions which do sample wells lead to short-lived HOCO and HCO2 complexes, in which either the H dissociates to produce highly excited overtone and combination states of CO2, or a CO bond breaks to give OH + CO having close to statistical vibrational-rotational distributions. Comparison of cross-sections and final-state distributions with experiment is excellent for the reactive collisions, and is good on a relative but not absolute basis for the non-reactive collisions.

Original languageEnglish
Pages (from-to)359-369
Number of pages11
JournalFaraday Discussions of the Chemical Society
Volume84
DOIs
Publication statusPublished - 1987

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Carbon Monoxide
Hydrogen
hydrogen atoms
chemistry
Atoms
collisions
excitation
Fourier transforms
Trajectories
Scattering
Experiments
saddle points
vibrational states
configuration interaction
vibration mode
trajectories
harmonics
expansion
cross sections
scattering

ASJC Scopus subject areas

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

Cite this

State-to-state chemistry with fast hydrogen atoms : Reaction and collisional excitation in H + CO2. / Schatz, George C; Fitzcharles, Michael S.; Harding, Lawrence B.

In: Faraday Discussions of the Chemical Society, Vol. 84, 1987, p. 359-369.

Research output: Contribution to journalArticle

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