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

doi:10.1021/jacs.7b10645

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

^*Corresponding author for this work

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

33 Scopus citations

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 (US)
Pages (from-to)	18664-18669
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	139
Issue number	51
DOIs	https://doi.org/10.1021/jacs.7b10645
State	Published - Dec 27 2017

Funding

L.R.M., G.C.S., and R.P.V.D. acknowledge support from the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space−Time Limit (CaSTL) Grant CHE-1414466. N.C., N.J., T.S., M.C.H., and R.P.V.D. acknowledge support from the Department of Energy Office of Basic Energy Sciences (SISGR Grant DE-FG02-09ER16109). E.A.P. and L.R.M. acknowledge support from the National Science Foundation Graduate Research Fellowship under Grant DGE-1324585 and the National Science Foundation Materials Research Science and Engineering Center (DMR-1121262). M.R.W. acknowledges the support of the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Department of Energy under grant No. DE- FG02-99ER14999. N.J. acknowledges support from startup funding of the University of Illinois at Chicago. L.R.M. G.C.S., and R.P.V.D. acknowledge support from the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CaSTL) Grant CHE-1414466. N.C., N.J., T.S., M.C.H., and R.P.V.D. acknowledge support from the Department of Energy Office of Basic Energy Sciences (SISGR Grant DE-FG02-09ER16109). E.A.P. and L.R.M. acknowledge support from the National Science Foundation Graduate Research Fellowship under Grant DGE-1324585 and the National Science Foundation Materials Research Science and Engineering Center (DMR-1121262). M.R.W. acknowledges the support of the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Department of Energy under grant No. DE-FG02-99ER14999. N.J. acknowledges support from startup funding of the University of Illinois at Chicago.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.7b10645

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Chiang, N., Jiang, N., Madison, L. R., Pozzi, E. A., Wasielewski, M. R., Ratner, M. A., Hersam, M. C., Seideman, T., Schatz, G. C., & Van Duyne, R. P. (2017). Probing Intermolecular Vibrational Symmetry Breaking in Self-Assembled Monolayers with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy. Journal of the American Chemical Society, 139(51), 18664-18669. https://doi.org/10.1021/jacs.7b10645

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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.}",

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Chiang, N, Jiang, N, Madison, LR, Pozzi, EA, Wasielewski, MR , Ratner, MA , Hersam, MC , Seideman, T , Schatz, GC & Van Duyne, RP 2017, 'Probing Intermolecular Vibrational Symmetry Breaking in Self-Assembled Monolayers with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy', Journal of the American Chemical Society, vol. 139, no. 51, pp. 18664-18669. https://doi.org/10.1021/jacs.7b10645

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

Abstract

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