Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy

Naihao Chiang; Nan Jiang; Dhabih V. Chulhai; Eric A. Pozzi; Mark C. Hersam; Lasse Jensen; Tamar Seideman; Richard P. Van Duyne

doi:10.1021/acs.nanolett.5b01225

Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy

Naihao Chiang, Nan Jiang, Dhabih V. Chulhai, Eric A. Pozzi, Mark C. Hersam, Lasse Jensen, Tamar Seideman, Richard P. Van Duyne

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

81 Scopus citations

Abstract

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 of meso-tetrakis- (3,5-ditertiarybutylphenyl)-porphyrin (H₂TBPP), chemical information regarding different vibronic excited states is revealed by a combination of theory and experiment; namely, TERS and time-dependent density functional theory (TDDFT) simulations. The observed TEF spectra suggest a weak coupling of H₂TBPP to the substrate due to the bulky t-butyl groups and a possible alternative excited state decay path. This work demonstrates the potential of combining TERS and TEF for studying surface-mounted porphyins on substrates, thus providing insight into porphyrin-sensitized solar cells and catalysis. (Figure Presented).

Original language	English (US)
Pages (from-to)	4114-4120
Number of pages	7
Journal	Nano letters
Volume	15
Issue number	6
DOIs	https://doi.org/10.1021/acs.nanolett.5b01225
State	Published - Jun 10 2015

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Publisher Copyright:
© 2015 American Chemical Society.

Keywords

time-dependent density functional theory (TDDFT)
tip-enhanced Raman spectroscopy (TERS)
tip-enhanced fluorescence (TEF)
ultrahigh vacuum scanning tunneling microscopy (UHV-STM)

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title = "Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy",

abstract = "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 of meso-tetrakis- (3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP), chemical information regarding different vibronic excited states is revealed by a combination of theory and experiment; namely, TERS and time-dependent density functional theory (TDDFT) simulations. The observed TEF spectra suggest a weak coupling of H2TBPP to the substrate due to the bulky t-butyl groups and a possible alternative excited state decay path. This work demonstrates the potential of combining TERS and TEF for studying surface-mounted porphyins on substrates, thus providing insight into porphyrin-sensitized solar cells and catalysis. (Figure Presented).",

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AU - Jiang, Nan

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AU - Pozzi, Eric A.

AU - Hersam, Mark C.

AU - Jensen, Lasse

AU - Seideman, Tamar

AU - Van Duyne, Richard P.

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AB - 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 of meso-tetrakis- (3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP), chemical information regarding different vibronic excited states is revealed by a combination of theory and experiment; namely, TERS and time-dependent density functional theory (TDDFT) simulations. The observed TEF spectra suggest a weak coupling of H2TBPP to the substrate due to the bulky t-butyl groups and a possible alternative excited state decay path. This work demonstrates the potential of combining TERS and TEF for studying surface-mounted porphyins on substrates, thus providing insight into porphyrin-sensitized solar cells and catalysis. (Figure Presented).

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Molecular-Resolution Interrogation of a Porphyrin Monolayer by Ultrahigh Vacuum Tip-Enhanced Raman and Fluorescence Spectroscopy

Abstract

Bibliographical note

Keywords

UN SDGs

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