A surface-enhanced hyper-Raman and surface-enhanced Raman scattering study of frans-1,2-bis(4-pyridyl)ethylene adsorbed onto silver film over nanosphere electrodes. Vibrational assignments

Experiment and theory

Wen Hui Yang, John Hulteen, George C Schatz, Richard P. Van Duyne

Research output: Contribution to journalArticle

183 Citations (Scopus)

Abstract

We present theoretical and experimental studies of the infrared (IR) spectroscopy, normal Raman spectroscopy (NRS), surface-enhanced Raman spectroscopy (SERS), and surface-enhanced hyper-Raman (SEHRS) spectroscopy of trans-1,2-bis(4-pyridyl)ethylene (BPE). This centrosymmetric molecule is expected to have no common Raman and hyper-Raman lines provided that it is not strongly perturbed by adsorption on the surface. The measured SERS spectrum, obtained under electrochemical conditions on Ag film over nanosphere (AgFON) electrodes, shows a well defined C=C stretch band that is not seen in the SEHRS spectrum, but many of the other bands overlap closely. We use ab initio calculations for isolated BPE to assign the spectra, and find excellent agreement between the calculated and measured IR and SERS spectra, and good agreement between the calculated and measured SEHRS spectrum. We find that the apparently overlapping IR, SERS, and SEHRS bands are in fact due to modes that have similar vibrational characteristics but different symmetry. Our results indicate that SEHRS spectra are consistent with the expected (three photon) selection rules and intensities. This rules out an alternative mechanism in which the observed spectrum arises from surface second harmonic generation (SHG) followed by SERS excited at the second harmonic frequency.

Original languageEnglish
Pages (from-to)4313-4323
Number of pages11
JournalJournal of Chemical Physics
Volume104
Issue number11
Publication statusPublished - 1996

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Nanospheres
Silver
Raman scattering
ethylene
Raman spectroscopy
silver
Raman spectra
Electrodes
electrodes
Experiments
Infrared radiation
Harmonic generation
Infrared spectroscopy
harmonic generations
Photons
infrared spectroscopy
harmonics
Adsorption
Molecules
adsorption

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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title = "A surface-enhanced hyper-Raman and surface-enhanced Raman scattering study of frans-1,2-bis(4-pyridyl)ethylene adsorbed onto silver film over nanosphere electrodes. Vibrational assignments: Experiment and theory",
abstract = "We present theoretical and experimental studies of the infrared (IR) spectroscopy, normal Raman spectroscopy (NRS), surface-enhanced Raman spectroscopy (SERS), and surface-enhanced hyper-Raman (SEHRS) spectroscopy of trans-1,2-bis(4-pyridyl)ethylene (BPE). This centrosymmetric molecule is expected to have no common Raman and hyper-Raman lines provided that it is not strongly perturbed by adsorption on the surface. The measured SERS spectrum, obtained under electrochemical conditions on Ag film over nanosphere (AgFON) electrodes, shows a well defined C=C stretch band that is not seen in the SEHRS spectrum, but many of the other bands overlap closely. We use ab initio calculations for isolated BPE to assign the spectra, and find excellent agreement between the calculated and measured IR and SERS spectra, and good agreement between the calculated and measured SEHRS spectrum. We find that the apparently overlapping IR, SERS, and SEHRS bands are in fact due to modes that have similar vibrational characteristics but different symmetry. Our results indicate that SEHRS spectra are consistent with the expected (three photon) selection rules and intensities. This rules out an alternative mechanism in which the observed spectrum arises from surface second harmonic generation (SHG) followed by SERS excited at the second harmonic frequency.",
author = "Yang, {Wen Hui} and John Hulteen and Schatz, {George C} and {Van Duyne}, {Richard P.}",
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T1 - A surface-enhanced hyper-Raman and surface-enhanced Raman scattering study of frans-1,2-bis(4-pyridyl)ethylene adsorbed onto silver film over nanosphere electrodes. Vibrational assignments

T2 - Experiment and theory

AU - Yang, Wen Hui

AU - Hulteen, John

AU - Schatz, George C

AU - Van Duyne, Richard P.

PY - 1996

Y1 - 1996

N2 - We present theoretical and experimental studies of the infrared (IR) spectroscopy, normal Raman spectroscopy (NRS), surface-enhanced Raman spectroscopy (SERS), and surface-enhanced hyper-Raman (SEHRS) spectroscopy of trans-1,2-bis(4-pyridyl)ethylene (BPE). This centrosymmetric molecule is expected to have no common Raman and hyper-Raman lines provided that it is not strongly perturbed by adsorption on the surface. The measured SERS spectrum, obtained under electrochemical conditions on Ag film over nanosphere (AgFON) electrodes, shows a well defined C=C stretch band that is not seen in the SEHRS spectrum, but many of the other bands overlap closely. We use ab initio calculations for isolated BPE to assign the spectra, and find excellent agreement between the calculated and measured IR and SERS spectra, and good agreement between the calculated and measured SEHRS spectrum. We find that the apparently overlapping IR, SERS, and SEHRS bands are in fact due to modes that have similar vibrational characteristics but different symmetry. Our results indicate that SEHRS spectra are consistent with the expected (three photon) selection rules and intensities. This rules out an alternative mechanism in which the observed spectrum arises from surface second harmonic generation (SHG) followed by SERS excited at the second harmonic frequency.

AB - We present theoretical and experimental studies of the infrared (IR) spectroscopy, normal Raman spectroscopy (NRS), surface-enhanced Raman spectroscopy (SERS), and surface-enhanced hyper-Raman (SEHRS) spectroscopy of trans-1,2-bis(4-pyridyl)ethylene (BPE). This centrosymmetric molecule is expected to have no common Raman and hyper-Raman lines provided that it is not strongly perturbed by adsorption on the surface. The measured SERS spectrum, obtained under electrochemical conditions on Ag film over nanosphere (AgFON) electrodes, shows a well defined C=C stretch band that is not seen in the SEHRS spectrum, but many of the other bands overlap closely. We use ab initio calculations for isolated BPE to assign the spectra, and find excellent agreement between the calculated and measured IR and SERS spectra, and good agreement between the calculated and measured SEHRS spectrum. We find that the apparently overlapping IR, SERS, and SEHRS bands are in fact due to modes that have similar vibrational characteristics but different symmetry. Our results indicate that SEHRS spectra are consistent with the expected (three photon) selection rules and intensities. This rules out an alternative mechanism in which the observed spectrum arises from surface second harmonic generation (SHG) followed by SERS excited at the second harmonic frequency.

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