Ultraviolet resonance Raman (UVRR) scattering is a highly sensitive and selective vibrational spectroscopic technique with a broad range of applications from polyaromatic hydrocarbons (PAHs) to biomolecular systems (peptides/proteins and nucleic acids) and catalysts. The interpretation of experimental UVRR spectra is not as straightforward as in purely vibrational Raman scattering (Placzek approximation) due to the involvement of higher lying electronic states and vibronic coupling. This necessitates the comparison with theoretical UVRR spectra computed by electronic structure calculations. Anthracene is an ideal model system for such a comparison between experiment and theory because it is rigid, symmetric, and of moderate size. By taking into account Herzberg–Teller contributions including Duschinsky effects, bulk solvent effects, and anharmonic contributions, a good qualitative agreement close to the resonance condition is achieved. The present study shows that within the framework of time-dependent density functional theory (TD-DFT), a general and robust approach for the analysis and interpretation of resonance Raman spectra of medium- to large-size molecules is available.

Ultraviolet resonance Raman spectroscopy of anthracene: Experiment and theory

Bloino J.
;
Barone V.
;
2021

Abstract

Ultraviolet resonance Raman (UVRR) scattering is a highly sensitive and selective vibrational spectroscopic technique with a broad range of applications from polyaromatic hydrocarbons (PAHs) to biomolecular systems (peptides/proteins and nucleic acids) and catalysts. The interpretation of experimental UVRR spectra is not as straightforward as in purely vibrational Raman scattering (Placzek approximation) due to the involvement of higher lying electronic states and vibronic coupling. This necessitates the comparison with theoretical UVRR spectra computed by electronic structure calculations. Anthracene is an ideal model system for such a comparison between experiment and theory because it is rigid, symmetric, and of moderate size. By taking into account Herzberg–Teller contributions including Duschinsky effects, bulk solvent effects, and anharmonic contributions, a good qualitative agreement close to the resonance condition is achieved. The present study shows that within the framework of time-dependent density functional theory (TD-DFT), a general and robust approach for the analysis and interpretation of resonance Raman spectra of medium- to large-size molecules is available.
2021
Settore CHIM/02 - Chimica Fisica
chemical calculations; polyaromatic hydrocarbon; Raman spectroscopy; resonance Raman; UVRR
File in questo prodotto:
File Dimensione Formato  
jrs.6223.pdf

accesso aperto

Descrizione: Articolo
Tipologia: Published version
Licenza: Creative Commons
Dimensione 3.17 MB
Formato Adobe PDF
3.17 MB Adobe PDF

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/106186
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 5
  • ???jsp.display-item.citation.isi??? 5
social impact