Resonance Raman scattering of rhodamine 6G as calculated by time-dependent density functional theory: Vibronic and solvent effects

Research output: Contribution to journalArticle

Abstract

The geometries, UV-vis absorption spectra, and resonance Raman (RR) intensities have been determined for the S1 and S3 excited states of rhodamine 6G (R6G) in vacuum and ethanol by means of DFT/TDDFT methodologies with the aim of better understanding the structures and properties of the excited states. The RR spectra have been simulated from the vibronic theory of RR scattering as well as within the short-time approximation, while the solvent effects have been modeled using the polarizable continuum model. The S1 and S3 states of R6G present UV-vis absorption bands with similar vibronic structure, i.e., a shoulder at smaller wavelengths, although this shoulder is relatively more intense and more sensitive to the solvent in the case of S3. These differences are corroborated by the larger geometry relaxations upon excitation for S3 and the fact that the charge transfer of S3 is reduced in ethanol. Moreover, the differences between S1 and S3 are magnified when considering the RR spectra. On one hand, the RR spectrum of R6G in resonance with the S0 → S1 transition presents many transitions of which the relative intensities strongly vary when the excitation wavelength gets closer to the maximum of absorption. The RR spectrum of R6G in resonance with S1 is however little influenced by the solvent. On the other hand, the RR spectrum of R6G in resonance with the S0 → S 3 transition displays only a few bands, strongly depends on the solvent, and is little affected when changing the excitation wavelength within the limits of the absorption band. As a consequence, the shorttime approximation is suitable to reproduce the RR spectrum of R6G in resonance with S3 for a broad range of excitation wavelengths, whereas the vibronic theory approach is needed for describing the RR spectrum of R6G in resonance with S1 close to resonance.

Original languageEnglish
Pages (from-to)3215-3223
Number of pages9
JournalJournal of physical chemistry A
Volume112
Issue number14
DOIs
Publication statusPublished - 10 Apr 2008

Fingerprint

resonance scattering
rhodamine
Density functional theory
Raman scattering
Raman spectra
density functional theory
excitation
Absorption spectra
Wavelength
shoulders
rhodamine 6G
absorption spectra
wavelengths
Excited states
ethyl alcohol
Ethanol
Geometry
geometry
approximation
Discrete Fourier transforms

Cite this

@article{bdc8c3d1d9244e72a5979e5ee055c4d1,
title = "Resonance Raman scattering of rhodamine 6G as calculated by time-dependent density functional theory: Vibronic and solvent effects",
abstract = "The geometries, UV-vis absorption spectra, and resonance Raman (RR) intensities have been determined for the S1 and S3 excited states of rhodamine 6G (R6G) in vacuum and ethanol by means of DFT/TDDFT methodologies with the aim of better understanding the structures and properties of the excited states. The RR spectra have been simulated from the vibronic theory of RR scattering as well as within the short-time approximation, while the solvent effects have been modeled using the polarizable continuum model. The S1 and S3 states of R6G present UV-vis absorption bands with similar vibronic structure, i.e., a shoulder at smaller wavelengths, although this shoulder is relatively more intense and more sensitive to the solvent in the case of S3. These differences are corroborated by the larger geometry relaxations upon excitation for S3 and the fact that the charge transfer of S3 is reduced in ethanol. Moreover, the differences between S1 and S3 are magnified when considering the RR spectra. On one hand, the RR spectrum of R6G in resonance with the S0 → S1 transition presents many transitions of which the relative intensities strongly vary when the excitation wavelength gets closer to the maximum of absorption. The RR spectrum of R6G in resonance with S1 is however little influenced by the solvent. On the other hand, the RR spectrum of R6G in resonance with the S0 → S 3 transition displays only a few bands, strongly depends on the solvent, and is little affected when changing the excitation wavelength within the limits of the absorption band. As a consequence, the shorttime approximation is suitable to reproduce the RR spectrum of R6G in resonance with S3 for a broad range of excitation wavelengths, whereas the vibronic theory approach is needed for describing the RR spectrum of R6G in resonance with S1 close to resonance.",
author = "Julien Guthmuller and Beno{\^i}t Champagne",
year = "2008",
month = "4",
day = "10",
doi = "10.1021/jp7112279",
language = "English",
volume = "112",
pages = "3215--3223",
journal = "The journal of physical chemistry. A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Resonance Raman scattering of rhodamine 6G as calculated by time-dependent density functional theory

T2 - Vibronic and solvent effects

AU - Guthmuller, Julien

AU - Champagne, Benoît

PY - 2008/4/10

Y1 - 2008/4/10

N2 - The geometries, UV-vis absorption spectra, and resonance Raman (RR) intensities have been determined for the S1 and S3 excited states of rhodamine 6G (R6G) in vacuum and ethanol by means of DFT/TDDFT methodologies with the aim of better understanding the structures and properties of the excited states. The RR spectra have been simulated from the vibronic theory of RR scattering as well as within the short-time approximation, while the solvent effects have been modeled using the polarizable continuum model. The S1 and S3 states of R6G present UV-vis absorption bands with similar vibronic structure, i.e., a shoulder at smaller wavelengths, although this shoulder is relatively more intense and more sensitive to the solvent in the case of S3. These differences are corroborated by the larger geometry relaxations upon excitation for S3 and the fact that the charge transfer of S3 is reduced in ethanol. Moreover, the differences between S1 and S3 are magnified when considering the RR spectra. On one hand, the RR spectrum of R6G in resonance with the S0 → S1 transition presents many transitions of which the relative intensities strongly vary when the excitation wavelength gets closer to the maximum of absorption. The RR spectrum of R6G in resonance with S1 is however little influenced by the solvent. On the other hand, the RR spectrum of R6G in resonance with the S0 → S 3 transition displays only a few bands, strongly depends on the solvent, and is little affected when changing the excitation wavelength within the limits of the absorption band. As a consequence, the shorttime approximation is suitable to reproduce the RR spectrum of R6G in resonance with S3 for a broad range of excitation wavelengths, whereas the vibronic theory approach is needed for describing the RR spectrum of R6G in resonance with S1 close to resonance.

AB - The geometries, UV-vis absorption spectra, and resonance Raman (RR) intensities have been determined for the S1 and S3 excited states of rhodamine 6G (R6G) in vacuum and ethanol by means of DFT/TDDFT methodologies with the aim of better understanding the structures and properties of the excited states. The RR spectra have been simulated from the vibronic theory of RR scattering as well as within the short-time approximation, while the solvent effects have been modeled using the polarizable continuum model. The S1 and S3 states of R6G present UV-vis absorption bands with similar vibronic structure, i.e., a shoulder at smaller wavelengths, although this shoulder is relatively more intense and more sensitive to the solvent in the case of S3. These differences are corroborated by the larger geometry relaxations upon excitation for S3 and the fact that the charge transfer of S3 is reduced in ethanol. Moreover, the differences between S1 and S3 are magnified when considering the RR spectra. On one hand, the RR spectrum of R6G in resonance with the S0 → S1 transition presents many transitions of which the relative intensities strongly vary when the excitation wavelength gets closer to the maximum of absorption. The RR spectrum of R6G in resonance with S1 is however little influenced by the solvent. On the other hand, the RR spectrum of R6G in resonance with the S0 → S 3 transition displays only a few bands, strongly depends on the solvent, and is little affected when changing the excitation wavelength within the limits of the absorption band. As a consequence, the shorttime approximation is suitable to reproduce the RR spectrum of R6G in resonance with S3 for a broad range of excitation wavelengths, whereas the vibronic theory approach is needed for describing the RR spectrum of R6G in resonance with S1 close to resonance.

UR - http://www.scopus.com/inward/record.url?scp=46749147542&partnerID=8YFLogxK

U2 - 10.1021/jp7112279

DO - 10.1021/jp7112279

M3 - Article

AN - SCOPUS:46749147542

VL - 112

SP - 3215

EP - 3223

JO - The journal of physical chemistry. A

JF - The journal of physical chemistry. A

SN - 1089-5639

IS - 14

ER -