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.
N1 - Funding Information:
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.
Funding Information:
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.
Publisher Copyright:
© 2017 American Chemical Society.
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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U2 - 10.1021/jacs.7b10645
DO - 10.1021/jacs.7b10645
M3 - Article
C2 - 29198112
AN - SCOPUS:85039926728
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 -