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Single‐Molecule Study of a Plasmon‐Induced Reaction for a Strongly Chemisorbed Molecule
Author(s) -
Kazuma Emiko,
Lee Minhui,
Jung Jaehoon,
Trenary Michael,
Kim Yousoo
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202001863
Subject(s) - antibonding molecular orbital , scanning tunneling microscope , chemical physics , molecule , plasmon , dissociation (chemistry) , density functional theory , chemistry , metal , photochemistry , chemical reaction , excitation , surface plasmon , atomic orbital , molecular physics , electronic structure , materials science , computational chemistry , nanotechnology , electron , physics , biochemistry , optoelectronics , organic chemistry , quantum mechanics
Chemical reactions induced by plasmons achieve effective solar‐to‐chemical energy conversion. However, the mechanism of these reactions, which generate a strong electric field, hot carriers, and heat through the excitation and decay processes, is still controversial. In addition, it is not fully understood which factor governs the mechanism. To obtain mechanistic knowledge, we investigated the plasmon‐induced dissociation of a single‐molecule strongly chemisorbed on a metal surface, two O 2 species chemisorbed on Ag(110) with different orientations and electronic structures, using a scanning tunneling microscope (STM) combined with light irradiation at 5 K. A combination of quantitative analysis by the STM and density functional theory calculations revealed that the hot carriers are transferred to the antibonding (π*) orbitals of O 2 strongly hybridized with the metal states and that the dominant pathway and reaction yield are determined by the electronic structures formed by the molecule–metal chemical interaction.