Photoinitiated reaction dynamics between aligned adsorbates on solid surfaces: A theoretical exploration of the H + CO2 system on LiF(001)

Josie V. Setzler, Hua Guo, George C Schatz

Research output: Contribution to journalArticle

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Abstract

We report a quasi-classical trajectory study of a chemical reaction between H and CO2 at the LiF(001) surface. The reaction is initiated by photodissociation of well-aligned HBr(ad) at 193 nm, which produces a "hot" H atom directed toward a nearby CO2(ad). Single molecules of each reactant are placed on a static surface, and a full-dimensional HCO2 potential derived from ab initio calculations is used. The adsorbate-substrate and the adsorbate-adsorbate potentials consist of both nonelectrostatic and electrostatic contributions. Several energetically favorable adsorption configurations are determined by a Monte Carlo method. Quasi-classical trajectories are calculated at 80 K for four different adsorption configurations. We find that the reactivity at some configurations is significantly enhanced compared with the corresponding gas-phase simulation. The calculated impact parameters and incident angles of the surface-aligned collisions indicate that the enhanced reactivity can be largely attributed to the closeness and alignment of the coadsorbates on the surface. Owing to the long-lived complex, product distributions, with the exception of a departure angle, show little memory with regard to the initial configuration and are similar to those obtained in the gas phase. A significant number of the unreacted hydrogen atoms retain sufficient energy to make subsequent reaction with other coadsorbates a possibility. We find evidence of several dynamic features pertinent to the use of the surface as a template for reactivity enhancement, including scattering at the surface, the squeezed atom effect, chattering, and caging.

Original languageEnglish
Pages (from-to)5352-5361
Number of pages10
JournalJournal of Physical Chemistry B
Volume101
Issue number27
Publication statusPublished - Jul 3 1997

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Adsorbates
solid surfaces
reactivity
configurations
Atoms
Gases
Trajectories
trajectories
vapor phases
Photodissociation
Adsorption
adsorption
photodissociation
Monte Carlo method
atoms
Chemical reactions
Hydrogen
Electrostatics
hydrogen atoms
chemical reactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Cite this

Photoinitiated reaction dynamics between aligned adsorbates on solid surfaces : A theoretical exploration of the H + CO2 system on LiF(001). / Setzler, Josie V.; Guo, Hua; Schatz, George C.

In: Journal of Physical Chemistry B, Vol. 101, No. 27, 03.07.1997, p. 5352-5361.

Research output: Contribution to journalArticle

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