Photodissociation dynamics of CH3I adsorbed on MgO(100): Theory and experiment

M. I. McCarthy, R. B. Gerber, K. A. Trentelman, Paul Strupp, D. Howard Fairbrother, Peter C Stair, Eric Weitz

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Theoretical and experimental results are compared for the 257 nm photolysis of methyl iodide adsorbed on an MgO(100) crystal. Molecular-dynamics calculations treat CH3I as a pseudodiatomic molecule and describe the geometry and the vibrational and librational frequencies of ground state CH3I on the surface of a solid at 125 K. The simulations modeled the photodissociation dynamics of the adsorbed species. The photoexcitation of CH3I at 257 nm is to the 3Q0 state which is, in turn, coupled to the 1Q1 state. The electronic surface coupling allows for two dissociation pathways, producing either ground- or excited-state iodine atoms in concert with ground-state methyl radicals. The I*/I branching ratio and the veloc-ity and angular distributions of both photofragments are predicted by the theory. A comparison is made between these predictions and experimental observation of the I*/I branching ratio, the velocity distribution of the methyl fragment, and the internal state distribution of the methyl. A substantial lowering of the I*/I ratio as compared to data from the gas-phase photodissociation studies is both predicted by theory and seen experimentally. Theoretical simulations attribute this change to efficient trapping of the I* photofragments by the surface. Further comparisons between the theoretical predictions and the experimental data support a model where the molecule is aligned perpendicular to the surface and the escape of iodine atoms from the surface following the photodissociation of adsorbed methyl iodide involves collisions with the surface.

Original languageEnglish
Pages (from-to)5168-5176
Number of pages9
JournalJournal of Chemical Physics
Volume97
Issue number7
Publication statusPublished - 1992

Fingerprint

Photodissociation
photodissociation
Ground state
Experiments
Iodine
iodides
iodine
ground state
Atoms
Molecules
Photoexcitation
Angular distribution
Photolysis
predictions
Velocity distribution
photoexcitation
Excited states
escape
atoms
photolysis

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

McCarthy, M. I., Gerber, R. B., Trentelman, K. A., Strupp, P., Fairbrother, D. H., Stair, P. C., & Weitz, E. (1992). Photodissociation dynamics of CH3I adsorbed on MgO(100): Theory and experiment. Journal of Chemical Physics, 97(7), 5168-5176.

Photodissociation dynamics of CH3I adsorbed on MgO(100) : Theory and experiment. / McCarthy, M. I.; Gerber, R. B.; Trentelman, K. A.; Strupp, Paul; Fairbrother, D. Howard; Stair, Peter C; Weitz, Eric.

In: Journal of Chemical Physics, Vol. 97, No. 7, 1992, p. 5168-5176.

Research output: Contribution to journalArticle

McCarthy, MI, Gerber, RB, Trentelman, KA, Strupp, P, Fairbrother, DH, Stair, PC & Weitz, E 1992, 'Photodissociation dynamics of CH3I adsorbed on MgO(100): Theory and experiment', Journal of Chemical Physics, vol. 97, no. 7, pp. 5168-5176.
McCarthy MI, Gerber RB, Trentelman KA, Strupp P, Fairbrother DH, Stair PC et al. Photodissociation dynamics of CH3I adsorbed on MgO(100): Theory and experiment. Journal of Chemical Physics. 1992;97(7):5168-5176.
McCarthy, M. I. ; Gerber, R. B. ; Trentelman, K. A. ; Strupp, Paul ; Fairbrother, D. Howard ; Stair, Peter C ; Weitz, Eric. / Photodissociation dynamics of CH3I adsorbed on MgO(100) : Theory and experiment. In: Journal of Chemical Physics. 1992 ; Vol. 97, No. 7. pp. 5168-5176.
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