Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 8, Pages 3115-3121Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b12680
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Funding
- National Research Foundation of Korea (NRF) [2015R1C1A1A01052947]
- US National Science Foundation [CHE-1464816]
- [15H02025]
- [16K17862]
- Grants-in-Aid for Scientific Research [15H02025] Funding Source: KAKEN
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1464816] Funding Source: National Science Foundation
- National Research Foundation of Korea [2015R1C1A1A01052947] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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We demonstrate molecular photodissociation on single-crystalline metal substrates, driven by visible-light irradiation. The visible-light-induced photodissociation on metal substrates has long been thought to never occur, either because visible-light energy is much smaller than the optical energy gap between the frontier electronic states of the molecule or because the molecular excited states have short lifetimes due to the strong hybridization between the adsorbate molecular orbitals (MOs) and metal substrate. The S-S bond in dimethyl disulfide adsorbed on both Cu(111) and Ag(111) surfaces was dissociated through direct electronic excitation from the HOMO-derived MO (the nonbonding lone-pair type orbitals on the S atoms (n(s)))to the LUMOderived MO (the antibonding orbital localized on the S-S bond (sigma*(ss))) by irradiation with visible light. A combination of scanning tunneling microscopy and density functional theory calculations revealed that visible-light-induced photodissociation becomes possible due to the interfacial electronic structures constructed by the hybridization between molecular orbitals and the metal substrate states. The molecule metal hybridization decreases the gap between the HOMO-and LUMO-derived MOs into the visible-light energy region and forms LUMO-derived MOs that have less overlap with the metal substrate, which results in longer excited-state lifetimes.
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