Adsorbate Dissociation Due to Heteromolecular Electronic Energy Transfer from Fluorobenzene Thin Films

Fuente: arXiv
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Autor principal: Jensen, E. T.
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Publicado: 2024
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author Jensen, E. T.
author_facet Jensen, E. T.
contents Study of the near-UV photodissociation dynamics for monolayer (ML) quantities of CH$_3$I on thin films of a series of fluorobenzenes and benzene (1--25ML) grown on a Cu(100) substrate finds that in addition to gas-phase-like neutral photodissociation, CH$_3$I dissociation can be enhanced via photoabsorption in several of the thin films studied. Distinct CH$_3$ photofragment kinetic energy distributions are found for CH$_3$I photodissociation on C$_6$H$_5$F, 1,4-C$_6$H$_4$F$_2$ and C$_6$H$_6$ thin films, and distinguished from neutral photodissociation pathways using polarized incident light. The effective photodissociation cross section for CH$_3$I on these thin films is increased as compared to that for the higher F-count fluorobenzene thin films due to the additional photodissociation pathway available. Quenching by the metal substrate of the photoexcitation via this new pathway suggests a significantly longer timescale for excitation than that of neutral CH$_3$I photodissociation. The observations support a mechanism in which neutral photoexcitation in the thin film (i.e. an exciton) is transported to the interface with CH$_3$I, and transferring the electronic excitation to the CH$_3$I which then dissociates. The unimodal CH$_3$ photofragment distribution and observed kinetic energies on the fluorobenzene thin films suggest that the dissociation occurs via the $^3Q_1$ excited state of CH$_3$I.
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id arxiv_https___arxiv_org_abs_2403_12277
institution arXiv
publishDate 2024
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spellingShingle Adsorbate Dissociation Due to Heteromolecular Electronic Energy Transfer from Fluorobenzene Thin Films
Jensen, E. T.
Chemical Physics
Other Condensed Matter
Study of the near-UV photodissociation dynamics for monolayer (ML) quantities of CH$_3$I on thin films of a series of fluorobenzenes and benzene (1--25ML) grown on a Cu(100) substrate finds that in addition to gas-phase-like neutral photodissociation, CH$_3$I dissociation can be enhanced via photoabsorption in several of the thin films studied. Distinct CH$_3$ photofragment kinetic energy distributions are found for CH$_3$I photodissociation on C$_6$H$_5$F, 1,4-C$_6$H$_4$F$_2$ and C$_6$H$_6$ thin films, and distinguished from neutral photodissociation pathways using polarized incident light. The effective photodissociation cross section for CH$_3$I on these thin films is increased as compared to that for the higher F-count fluorobenzene thin films due to the additional photodissociation pathway available. Quenching by the metal substrate of the photoexcitation via this new pathway suggests a significantly longer timescale for excitation than that of neutral CH$_3$I photodissociation. The observations support a mechanism in which neutral photoexcitation in the thin film (i.e. an exciton) is transported to the interface with CH$_3$I, and transferring the electronic excitation to the CH$_3$I which then dissociates. The unimodal CH$_3$ photofragment distribution and observed kinetic energies on the fluorobenzene thin films suggest that the dissociation occurs via the $^3Q_1$ excited state of CH$_3$I.
title Adsorbate Dissociation Due to Heteromolecular Electronic Energy Transfer from Fluorobenzene Thin Films
topic Chemical Physics
Other Condensed Matter
url https://arxiv.org/abs/2403.12277