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Evaluating Plasmonic Transport in Current-carrying Silver Nanowires
Published on: December 11, 2013
Quantifying Ultrafast Hot Carrier Transfer along a Specific Vibrational Reaction Coordinate at Plasmonic
Quanbing Pei1, Junjun Tan2, Jing Lai1
1Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.
None:
Insight into the transfer of energetic hot carriers (HCs) from plasmonic nanostructures to specific vibrational coordinates of adsorbed molecules is essential for understanding the HC-driven reaction mechanism, yet this process remains incompletely elucidated. Here, using 4-nitrothiophenol (4-NTP) adsorbed on gold nanoparticles (AuNPs) as a model system, we demonstrate that femtosecond visible pump-sum frequency generation vibrational spectroscopy (SFG-VS) probe technique can quantitatively monitor ultrafast interfacial HC injection into 4-NTP molecules following AuNP excitation, by detecting the third-order nonlinear SFG response (χ(3)) of specific vibrational modes. The HC transfer efficiencies from AuNPs to the NO2 coordinates are determined to be 45-55% and 21-23% for interband and intraband excitations, respectively, significantly higher than those to the C═C coordinates. A higher HC transfer efficiency is correlated with an enhanced reaction yield. The observed selectivity in HC transfer to specific vibrational coordinates highlights the dominance of nonthermal pathways in plasmonic catalysis.
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