Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 41, Pages 13740-13749Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b08725
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Funding
- Natural Science Foundation of Science of China [11322434, 21121003, 11620101003, 21503248, 21543008, 21673266]
- Chinese Department of Science Technology [2016YFA0200600, 2016YFA0200604]
- National Science Foundation [CHE-1213189, CHE-1565704]
- Natural Science Foundation of Shandong Province for Distinguished Young Scholars [JQ201504]
- U.S. Department of Energy [DE-SC0014429]
- DOE Office of Biological and Environmental Research
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1565704] Funding Source: National Science Foundation
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Photogenerated charge carrier dynamics near molecule/TiO2 interfaces are important for the photocatalytic and photovoltaic processes. To understand this fundamental aspect, we performed a time-domain ab initio nonadiabatic molecular dynamics study of the photogenerated hole dynamics at the CH3OH/rutile TiO2(110) interface. We studied the forward and reverse hole transfer between TiO2 and CH3OH as well as the hole energy relaxation to the valence band maximum. First, we show that the hole-trapping ability of CH3OH depends strongly on the adsorption structure. Only when the CH3OH is deprotonated to form chemisorbed CH3O will 45% of the hole be trapped by the molecule. Second, we find that strong fluctuations of the HOMO energies of the adsorbed molecules induced by electron phonon coupling provide additional channels, which accelerate the hole energy relaxation. Third, we demonstrate that the charge transfer and energy relaxation processes depend significantly on temperature. When the temperature decreases from 100 to 30 K, the forward hole transfer and energy relaxation processes are strongly suppressed because of the reduction of phonon occupation. These results indicate that the molecule/TiO2 energy level alignment, thermal excitation of a phonon, and electron phonon coupling are the key factors that determine the photogenerated hole dynamics. Our studies provide valuable insights into the photogenerated charge and energy transfer dynamics at molecule/semiconductor interfaces.
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