Resonance Raman scattering of rhodamine 6G as calculated using time-dependent density functional theory

Lasse Jensen, George C Schatz

Research output: Contribution to journalArticle

249 Citations (Scopus)

Abstract

In this work, we present the first calculation of the resonance Raman scattering (RRS) spectrum of rhodamine 6G (R6G) which is a prototype molecule in surface-enhanced Raman scattering (SERS). The calculation is done using a recently developed time-dependent density functional theory (TDDFT) method, which uses a short-time approximation to evaluate the Raman scattering cross section. The normal Raman spectrum calculated with this method is in good agreement with experimental results. The calculated RRS spectrum shows qualitative agreement with SERS results at a wavelength that corresponds to excitation of the Si state, but there are significant differences with the measured RRS spectrum at wavelengths that correspond to excitation of the vibronic sideband of Si. Although the agreement with the experiments is not perfect, the results provide insight into the RRS spectrum of R6G at wavelengths close to the absorption maximum where experiments are hindered due to strong fluorescence. The calculated resonance enhancements are found to be on the order of 105. This indicates that a surface enhancement factor of about 10 10 would be required in SERS in order to achieve single-molecule detection of R6G.

Original languageEnglish
Pages (from-to)5973-5977
Number of pages5
JournalJournal of Physical Chemistry A
Volume110
Issue number18
DOIs
Publication statusPublished - May 11 2006

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resonance scattering
rhodamine
Density functional theory
Raman scattering
Raman spectra
density functional theory
Wavelength
wavelengths
rhodamine 6G
Molecules
augmentation
sidebands
scattering cross sections
excitation
molecules
Experiments
Fluorescence
prototypes
fluorescence
approximation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Resonance Raman scattering of rhodamine 6G as calculated using time-dependent density functional theory. / Jensen, Lasse; Schatz, George C.

In: Journal of Physical Chemistry A, Vol. 110, No. 18, 11.05.2006, p. 5973-5977.

Research output: Contribution to journalArticle

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