Resonance Raman and vibronic absorption spectra with Duschinsky rotation from a time-dependent perspective application to beta-carotene
- The time-dependent approach to electronic spectroscopy, as popularized by Heller and co-workers in the 1980s, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption and resonance Raman spectra of beta-carotene, with and without a solvent. Two-state models, the harmonic and the Condon approximations are used in order to do so. A new code has been developed which includes excited state displacements, vibrational frequency shifts, and Duschinsky rotation, i.e., mode mixing, for both non-adiabatic spectroscopies. It is shown that Duschinsky rotation has a pronounced effect on the resonance Raman spectra of beta-carotene. In particular, it can explain a recently found anomalous behaviour of the so-called nu(1) peak in resonance Raman spectra [N. Tschirner, M. Schenderlein, K. Brose, E. Schlodder, M. A. Mroginski, C. Thomsen, and P. Hildebrandt, Phys. Chem. Chem. Phys. 11, 11471 (2009)], which shifts with the change in excitation wavelength.
Author details: | Shiladitya Banerjee, Dominik Kröner, Peter SaalfrankORCiDGND |
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DOI: | https://doi.org/10.1063/1.4748147 |
ISSN: | 0021-9606 |
Title of parent work (English): | The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr |
Publisher: | American Institute of Physics |
Place of publishing: | Melville |
Publication type: | Article |
Language: | English |
Year of first publication: | 2012 |
Publication year: | 2012 |
Release date: | 2017/03/26 |
Volume: | 137 |
Issue: | 22 |
Number of pages: | 9 |
Funding institution: | Deutsche Forschungsgemeinschaft; Leibniz Graduate School 'Dynamics in new Light'; Cluster of Excellence 304 "Unifying Concepts in Catalysis" |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie |
Peer review: | Referiert |