Substrate mediated photochemistry on a molecular surface: OCS on Ag clusters

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DOIResolve DOI: http://doi.org/10.1063/1.476818
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TypeArticle
Journal titleThe Journal of Chemical Physics
ISSN0021-9606
Volume109
Issue6
Pages2474
Subjectsilver; photochemistry; surface photochemistry; desorption; adsorbates
AbstractThe photochemistry of carbonyl sulfide (OCS) adsorbed to small silverclusters is shown to exhibit a striking odd–even dependence on the number of Ag atoms in the cluster. OCS is found to desorb nondissociatively from even numbered silverclusters. In contrast, on odd silverclusters, a new product channel corresponding to AgₙS is observed. Parallels are found with the photochemistry of adsorbates on extended surfaces. Cross-section measurements for OCS desorption from Ag₁₀ and wavelength-dependent measurements of OCS dissociation on Ag₉ both indicate that electronic excitation of the cluster initiates chemistry, analogous to substrate mediated surface photochemistry. The size dependence is reasonably explained in terms of a charge-transfer mechanism involving an ion-pair state of the AgₙOCS complex.
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PublisherAIP Publishing
LanguageEnglish
AffiliationNational Research Council Canada; Human Health Therapeutics; Security and Disruptive Technologies
Peer reviewedYes
NPARC number21277564
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Record identifier40bafb55-f87b-422e-8300-32f0c74509b0
Record created2016-04-19
Record modified2017-03-23
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