Albert, J;
Falge, M;
Gomez, S;
Sola, IR;
Hildenbrand, H;
Engel, V;
(2015)
Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion.
The Journal of Chemical Physics
, 143
(4)
, Article 041102. 10.1063/1.4927396.
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Abstract
We theoretically investigate the photon-echo spectroscopy of coupled electron-nuclear quantum dynamics. Two situations are treated. In the first case, the Born-Oppenheimer (adiabatic) approximation holds. It is then possible to interpret the two-dimensional (2D) spectra in terms of vibrational motion taking place in different electronic states. In particular, pure vibrational coherences which are related to oscillations in the time-dependent third-order polarization can be identified. This concept fails in the second case, where strong non-adiabatic coupling leads to the breakdown of the Born-Oppenheimer-approximation. Then, the 2D-spectra reveal a complicated vibronic structure and vibrational coherences cannot be disentangled from the electronic motion.
| Type: | Article |
|---|---|
| Title: | Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/1.4927396 |
| Publisher version: | https://doi.org/10.1063/1.4927396 |
| Language: | English |
| Additional information: | This version is the version of record. For information on re-use, please refer to the publisher’s terms and conditions. |
| Keywords: | Optical fibers, Spectroscopy, Electronic coupling, Born-Oppenheimer approximation, Vibrational states, Adiabatic theorem, Quantum mechanical principles, Potential energy surfaces, Electrostatics, Schrodinger equations |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10085695 |
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