Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion
- Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Str. 42, Campus Nord, Am Hubland, 97074 Würzburg (Germany)
- Departamento de Quimica Fisica, Universidad Complutense, 28040 Madrid (Spain)
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.
- OSTI ID:
- 22493438
- Journal Information:
- Journal of Chemical Physics, Vol. 143, Issue 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
ADIABATIC APPROXIMATION
BORN-OPPENHEIMER APPROXIMATION
COUPLING
ELECTRONIC STRUCTURE
ELECTRONS
OSCILLATIONS
PHOTONS
POLARIZATION
TIME DEPENDENCE
TWO-DIMENSIONAL CALCULATIONS
TWO-DIMENSIONAL SYSTEMS
VIBRATIONAL STATES