Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 27th March 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 19, 2015
Previous Article Next Article

Two-dimensional electronic-vibrational spectra: modeling correlated electronic and nuclear motion

Author affiliations

Abstract

We calculate 2D electronic-vibrational (2D-EV) spectra of solvated organic dyes modeled in terms of a reduced set of electronic diabatic states (the essential states) non-adiabatically coupled to molecular vibrations. An effective overdamped coordinate, whose dynamics is described by the Smoluchowski diffusion equation, accounts for polar solvation. Results are discussed for two dyes with distinctively different spectroscopic behavior: 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) and 8-(N,N-dibutylamino)-2-azachrysene (AAC). Linear absorption and fluorescence spectra of DCM are well reproduced based on a minimal two-state model. The same model leads to 2D-EV spectra in good agreement with the recent experimental data reported by Oliver and coworkers for DCM in DMSO. In contrast, linear spectra of AAC show a subtle interplay between a locally-excited (LE) and a charge-transfer (CT) excitation, calling for a three-state model. Calculated 2D-EV spectra for AAC show a qualitatively different behavior, demonstrating that the experimental data for DCM do not support a LE/CT interplay. This resolves the long-lasting discussion about the nature of low-lying excitations of DCM in favor of the simplest picture.

Graphical abstract: Two-dimensional electronic-vibrational spectra: modeling correlated electronic and nuclear motion

Back to tab navigation

Supplementary files

Publication details

The article was received on 13 Mar 2015, accepted on 20 Apr 2015 and first published on 20 Apr 2015


Article type: Paper
DOI: 10.1039/C5CP01485A
Author version
available:
Download author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 13074-13081

  •   Request permissions

    Two-dimensional electronic-vibrational spectra: modeling correlated electronic and nuclear motion

    F. Terenziani and A. Painelli, Phys. Chem. Chem. Phys., 2015, 17, 13074
    DOI: 10.1039/C5CP01485A

Search articles by author

Spotlight

Advertisements