Photodissociation of CH{sub 3}Cl, C{sub 2}H{sub 5}Cl, and C{sub 6}H{sub 5}Cl on the Ag(111) surface: Ab initio embedded cluster and configuration interaction study

Journal Article · Sun Feb 21 00:00:00 EST 2010 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3322289· OSTI ID:21559835

Kokh, Daria B; Liebermann, Heinz-Peter; Buenker, Robert J ^[1]

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1. Theoretische Chemie, Fachbereich C, Bergische Universitaet Wuppertal, Gaussstr. 20, D-Wuppertal 42097 (Germany)

We report a comparative study of the photoinduced C-Cl bond cleavage in three Rd-Cl molecules (Rd=CH{sub 3}, C{sub 2}H{sub 5}, and C{sub 6}H{sub 5} radicals) on the Ag(111) surface. The ground, lowest excited states as well as anion states of adsorbed molecules have been computed at their equilibrium geometry and along the C-Cl dissociation pathway using the ab initio embedded cluster and multireference configuration interaction methods. The anion state can be formed by photoinduced electron transfer from the substrate to an adsorbate and is strongly bound to the surface in contrast with the electronic states of the adsorbate itself, which are only weakly perturbed by the silver surface. The excitation energy of the anion state lies lower in the Franck-Condon region than that of the lowest singlet excited state for all adsorbates and correlates directly with the dissociation products: adsorbed chlorine atom and the gas phase or adsorbed radical for Rd=CH{sub 3}, C{sub 2}H{sub 5}, and C{sub 6}H{sub 5}, respectively. The computed redshift of the photodissociation spectrum for the substrate-mediated photodissociation process relative to the corresponding gas-phase reaction is {approx}2 eV for CH{sub 3}Cl and C{sub 2}H{sub 5}Cl, and {approx}1 eV for C{sub 6}H{sub 5}Cl, which result is in good agreement with experimental data.

• OSTI ID: 21559835
• Journal Information: Journal of Chemical Physics, Vol. 132, Issue 7; Other Information: DOI: 10.1063/1.3322289; (c) 2010 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ADSORPTION
ANIONS
CHARGE EXCHANGE
CHEMICAL BONDS
CHLORINE
CLEAVAGE
CONFIGURATION INTERACTION
DISSOCIATION
ELECTRON TRANSFER
EXCITATION
EXCITED STATES
GROUND STATES
METHYL CHLORIDE
MOLECULAR STRUCTURE
PHOTOLYSIS
RADICALS
RED SHIFT
SILVER
SILVER 111
SURFACES
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHARGED PARTICLES
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
DAYS LIVING RADIOISOTOPES
DECOMPOSITION
ELEMENTS
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
IONS
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
METALS
MICROSTRUCTURE
MINUTES LIVING RADIOISOTOPES
NONMETALS
NUCLEI
ODD-EVEN NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIOISOTOPES
SILVER ISOTOPES
SORPTION
TRANSITION ELEMENTS