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Molecular Coupling between Organic Molecules and Metal

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journal contribution
posted on 24.08.2018, 00:00 by Pengcheng Hu, Xu Li, Bolin Li, Xiaofeng Han, Furong Zhang, Keng C. Chou, Zhan Chen, Xiaolin Lu
Molecular couplings at interfaces play important roles in determining the performance of nanophotonics and molecular electronics. In this Letter, using femtosecond sum frequency generation to trace free-induction decay of vibrationally excited aromatic thiol molecules immobilized on metal with and without the bridged methylene group(s), metal surface free electron-coupled and uncoupled phenyl C–H stretching vibrational modes were identified, with dephasing times of ∼0.28 and ∼0.60 ps, respectively. For thiols on Au with the bridged methylene group(s) (benzyl mercaptan and phenylethanethiol), both the coupled and uncoupled modes were observed; for thiol on Au without the bridged methylene group (thiophenol), only the coupled mode was observed. This indicates that the bridged methylene group(s) serving as a spacer can be used to adjust the molecular coupling between the phenyl vibration and surface free electrons. The experimental approach can be used to tune molecular couplings in advanced nanophotonics and molecular electronics.