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 language | English |
|---|---|
| Pages (from-to) | 18664-18669 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 51 |
| DOIs | |
| Publication status | Published - Dec 27 2017 |
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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 journal › Article
}
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.
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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 -