The origin of relative intensity fluctuations in single-molecule tip-enhanced Raman spectroscopy

Matthew D. Sonntag, Dhabih Chulhai, Tamar Seideman, Lasse Jensen, Richard P. Van Duyne

Research output: Contribution to journalArticle

75 Citations (Scopus)

Abstract

An explanation of the relative intensity fluctuations observed in single-molecule Raman experiments is described utilizing both single-molecule tip-enhanced Raman spectroscopy and time-dependent density functional theory calculations. No correlation is observed in mode to mode intensity fluctuations indicating that the changes in mode intensities are completely independent. Theoretical calculations provide convincing evidence that the fluctuations are not the result of diffusion, orientation, or local electromagnetic field gradients but rather are the result of subtle variations of the excited-state lifetime, energy, and geometry of the molecule. These variations in the excited-state properties will provide information on adsorbate-adsorbate and adsorbate-substrate interactions and may allow for inversion of experimental results to obtain these excited-state properties.

Original languageEnglish (US)
Pages (from-to)17187-17192
Number of pages6
JournalJournal of the American Chemical Society
Volume135
Issue number45
DOIs
StatePublished - Nov 13 2013

Fingerprint

Electromagnetic Fields
Raman Spectrum Analysis
Adsorbates
Excited states
Raman spectroscopy
Molecules
Electromagnetic fields
Density functional theory
Geometry
Substrates
Experiments

All Science Journal Classification (ASJC) codes

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

Cite this

Sonntag, Matthew D. ; Chulhai, Dhabih ; Seideman, Tamar ; Jensen, Lasse ; Van Duyne, Richard P. / The origin of relative intensity fluctuations in single-molecule tip-enhanced Raman spectroscopy. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 45. pp. 17187-17192.
@article{bfe3cf5daa724225806a81c679f19613,
title = "The origin of relative intensity fluctuations in single-molecule tip-enhanced Raman spectroscopy",
abstract = "An explanation of the relative intensity fluctuations observed in single-molecule Raman experiments is described utilizing both single-molecule tip-enhanced Raman spectroscopy and time-dependent density functional theory calculations. No correlation is observed in mode to mode intensity fluctuations indicating that the changes in mode intensities are completely independent. Theoretical calculations provide convincing evidence that the fluctuations are not the result of diffusion, orientation, or local electromagnetic field gradients but rather are the result of subtle variations of the excited-state lifetime, energy, and geometry of the molecule. These variations in the excited-state properties will provide information on adsorbate-adsorbate and adsorbate-substrate interactions and may allow for inversion of experimental results to obtain these excited-state properties.",
author = "Sonntag, {Matthew D.} and Dhabih Chulhai and Tamar Seideman and Lasse Jensen and {Van Duyne}, {Richard P.}",
year = "2013",
month = "11",
day = "13",
doi = "10.1021/ja408758j",
language = "English (US)",
volume = "135",
pages = "17187--17192",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "45",

}

The origin of relative intensity fluctuations in single-molecule tip-enhanced Raman spectroscopy. / Sonntag, Matthew D.; Chulhai, Dhabih; Seideman, Tamar; Jensen, Lasse; Van Duyne, Richard P.

In: Journal of the American Chemical Society, Vol. 135, No. 45, 13.11.2013, p. 17187-17192.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The origin of relative intensity fluctuations in single-molecule tip-enhanced Raman spectroscopy

AU - Sonntag, Matthew D.

AU - Chulhai, Dhabih

AU - Seideman, Tamar

AU - Jensen, Lasse

AU - Van Duyne, Richard P.

PY - 2013/11/13

Y1 - 2013/11/13

N2 - An explanation of the relative intensity fluctuations observed in single-molecule Raman experiments is described utilizing both single-molecule tip-enhanced Raman spectroscopy and time-dependent density functional theory calculations. No correlation is observed in mode to mode intensity fluctuations indicating that the changes in mode intensities are completely independent. Theoretical calculations provide convincing evidence that the fluctuations are not the result of diffusion, orientation, or local electromagnetic field gradients but rather are the result of subtle variations of the excited-state lifetime, energy, and geometry of the molecule. These variations in the excited-state properties will provide information on adsorbate-adsorbate and adsorbate-substrate interactions and may allow for inversion of experimental results to obtain these excited-state properties.

AB - An explanation of the relative intensity fluctuations observed in single-molecule Raman experiments is described utilizing both single-molecule tip-enhanced Raman spectroscopy and time-dependent density functional theory calculations. No correlation is observed in mode to mode intensity fluctuations indicating that the changes in mode intensities are completely independent. Theoretical calculations provide convincing evidence that the fluctuations are not the result of diffusion, orientation, or local electromagnetic field gradients but rather are the result of subtle variations of the excited-state lifetime, energy, and geometry of the molecule. These variations in the excited-state properties will provide information on adsorbate-adsorbate and adsorbate-substrate interactions and may allow for inversion of experimental results to obtain these excited-state properties.

UR - http://www.scopus.com/inward/record.url?scp=84887710852&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84887710852&partnerID=8YFLogxK

U2 - 10.1021/ja408758j

DO - 10.1021/ja408758j

M3 - Article

C2 - 24079659

AN - SCOPUS:84887710852

VL - 135

SP - 17187

EP - 17192

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 45

ER -