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Real-space and real-time observation of a plasmon-induced chemical reaction of a single molecule
Kazuma, Emiko,Jung, Jaehoon,Ueba, Hiromu,Trenary, Michael,Kim, Yousoo American Association for the Advancement of Scienc 2018 Science Vol.360 No.6388
<P>Plasmon-induced chemical reactions of molecules adsorbed on metal nanostructures are attracting increased attention for photocatalytic reactions. However, the mechanism remains controversial because of the difficulty of direct observation of the chemical reactions in the plasmonic field, which is strongly localized near the metal surface. We used a scanning tunneling microscope (STM) to achieve real-space and real-time observation of a plasmon-induced chemical reaction at the single-molecule level. A single dimethyl disulfide molecule on silver and copper surfaces was dissociated by the optically excited plasmon at the STM junction. The STM study combined with theoretical calculations shows that this plasmon-induced chemical reaction occurred by a direct intramolecular excitation mechanism.</P>
Direct Pathway to Molecular Photodissociation on Metal Surfaces Using Visible Light
Kazuma, Emiko,Jung, Jaehoon,Ueba, Hiromu,Trenary, Michael,Kim, Yousoo American Chemical Society 2017 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.139 No.8
<P>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.</P>