Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy.
作者： Naihao Chiang , Nan Jiang , Dhabih V. Chulhai , Eric A. Pozzi , Mark C. Hersam
DOI: 10.1021/ACS.NANOLETT.5B01225
关键词: Fluorescence spectroscopy 、 Raman spectroscopy 、 Time-dependent density functional theory 、 Scanning tunneling microscope 、 Density functional theory 、 Analytical chemistry 、 Molecular physics 、 Excited state 、 Raman scattering 、 Monolayer 、 Chemistry
摘要: Tip-enhanced Raman scattering (TERS) and optically excited tip-enhanced fluorescence (TEF) of a self-assembled porphyrin monolayer on Ag(111) are studied using an ultrahigh vacuum scanning tunneling microscope (UHV-STM). Through selectively exciting different Q-bands meso-tetrakis- (3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP), chemical information regarding vibronic states is revealed by combination theory experiment; namely, TERS time-dependent density functional (TDDFT) simulations. The observed TEF spectra suggest weak coupling H2TBPP to the substrate due bulky t-butyl groups possible alternative state decay path. This work demonstrates potential combining for studying surface-mounted porphyins substrates, thus providing insight into porphyrin-sensitized solar cells catalysis.
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