Probing Intermolecular Vibrational Symmetry Breaking in Self-Assembled Monolayers with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy

Naihao Chiang, Nan Jiang, Lindsey R. Madison, Eric A. Pozzi, Michael R Wasielewski, Mark A Ratner, Mark C Hersam, Tamar Seideman, George C Schatz, Richard P. Van Duyne

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) combines the atomic-scale imaging capability of scanning probe microscopy with the single-molecule chemical sensitivity and structural specificity of surface-enhanced Raman spectroscopy. Here, we use these techniques in combination with theory to reveal insights into the influence of intermolecular interactions on the vibrational spectra of a N-N′-bis(2,6-diisopropylphenyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI) self-assembled monolayer adsorbed on single-crystal Ag substrates at room temperature. In particular, we have revealed the lifting of a vibrational degeneracy of a mode of PDI on Ag(111) and Ag(100) surfaces, with the most strongly perturbed mode being that associated with the largest vibrational amplitude on the periphery of the molecule. This work demonstrates that UHV-TERS enables direct measurement of molecule-molecule interaction at nanoscale. We anticipate that this information will advance the fundamental understanding of the most important effect of intermolecular interactions on the vibrational modes of surface-bound molecules.

Original languageEnglish
Pages (from-to)18664-18669
Number of pages6
JournalJournal of the American Chemical Society
Volume139
Issue number51
DOIs
Publication statusPublished - Dec 27 2017

Fingerprint

Raman Spectrum Analysis
Ultrahigh vacuum
Self assembled monolayers
Vacuum
Raman spectroscopy
Molecules
Scanning Probe Microscopy
Perylene
Scanning probe microscopy
Sensitivity and Specificity
Vibrational spectra
Temperature
Single crystals
Imaging techniques
Substrates

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Probing Intermolecular Vibrational Symmetry Breaking in Self-Assembled Monolayers with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy. / Chiang, Naihao; Jiang, Nan; Madison, Lindsey R.; Pozzi, Eric A.; Wasielewski, Michael R; Ratner, Mark A; Hersam, Mark C; Seideman, Tamar; Schatz, George C; Van Duyne, Richard P.

In: Journal of the American Chemical Society, Vol. 139, No. 51, 27.12.2017, p. 18664-18669.

Research output: Contribution to journalArticle

@article{82af576b5d154099be37fa0c705fc4a3,
title = "Probing Intermolecular Vibrational Symmetry Breaking in Self-Assembled Monolayers with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy",
abstract = "Ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) combines the atomic-scale imaging capability of scanning probe microscopy with the single-molecule chemical sensitivity and structural specificity of surface-enhanced Raman spectroscopy. Here, we use these techniques in combination with theory to reveal insights into the influence of intermolecular interactions on the vibrational spectra of a N-N′-bis(2,6-diisopropylphenyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI) self-assembled monolayer adsorbed on single-crystal Ag substrates at room temperature. In particular, we have revealed the lifting of a vibrational degeneracy of a mode of PDI on Ag(111) and Ag(100) surfaces, with the most strongly perturbed mode being that associated with the largest vibrational amplitude on the periphery of the molecule. This work demonstrates that UHV-TERS enables direct measurement of molecule-molecule interaction at nanoscale. We anticipate that this information will advance the fundamental understanding of the most important effect of intermolecular interactions on the vibrational modes of surface-bound molecules.",
author = "Naihao Chiang and Nan Jiang and Madison, {Lindsey R.} and Pozzi, {Eric A.} and Wasielewski, {Michael R} and Ratner, {Mark A} and Hersam, {Mark C} and Tamar Seideman and Schatz, {George C} and {Van Duyne}, {Richard P.}",
year = "2017",
month = "12",
day = "27",
doi = "10.1021/jacs.7b10645",
language = "English",
volume = "139",
pages = "18664--18669",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "51",

}

TY - JOUR

T1 - Probing Intermolecular Vibrational Symmetry Breaking in Self-Assembled Monolayers with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy

AU - Chiang, Naihao

AU - Jiang, Nan

AU - Madison, Lindsey R.

AU - Pozzi, Eric A.

AU - Wasielewski, Michael R

AU - Ratner, Mark A

AU - Hersam, Mark C

AU - Seideman, Tamar

AU - Schatz, George C

AU - Van Duyne, Richard P.

PY - 2017/12/27

Y1 - 2017/12/27

N2 - Ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) combines the atomic-scale imaging capability of scanning probe microscopy with the single-molecule chemical sensitivity and structural specificity of surface-enhanced Raman spectroscopy. Here, we use these techniques in combination with theory to reveal insights into the influence of intermolecular interactions on the vibrational spectra of a N-N′-bis(2,6-diisopropylphenyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI) self-assembled monolayer adsorbed on single-crystal Ag substrates at room temperature. In particular, we have revealed the lifting of a vibrational degeneracy of a mode of PDI on Ag(111) and Ag(100) surfaces, with the most strongly perturbed mode being that associated with the largest vibrational amplitude on the periphery of the molecule. This work demonstrates that UHV-TERS enables direct measurement of molecule-molecule interaction at nanoscale. We anticipate that this information will advance the fundamental understanding of the most important effect of intermolecular interactions on the vibrational modes of surface-bound molecules.

AB - Ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) combines the atomic-scale imaging capability of scanning probe microscopy with the single-molecule chemical sensitivity and structural specificity of surface-enhanced Raman spectroscopy. Here, we use these techniques in combination with theory to reveal insights into the influence of intermolecular interactions on the vibrational spectra of a N-N′-bis(2,6-diisopropylphenyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI) self-assembled monolayer adsorbed on single-crystal Ag substrates at room temperature. In particular, we have revealed the lifting of a vibrational degeneracy of a mode of PDI on Ag(111) and Ag(100) surfaces, with the most strongly perturbed mode being that associated with the largest vibrational amplitude on the periphery of the molecule. This work demonstrates that UHV-TERS enables direct measurement of molecule-molecule interaction at nanoscale. We anticipate that this information will advance the fundamental understanding of the most important effect of intermolecular interactions on the vibrational modes of surface-bound molecules.

UR - http://www.scopus.com/inward/record.url?scp=85039926728&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85039926728&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b10645

DO - 10.1021/jacs.7b10645

M3 - Article

VL - 139

SP - 18664

EP - 18669

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 51

ER -