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Title: Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion

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.
Authors:
; ; ;  [1] ; ;  [2]
  1. Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Str. 42, Campus Nord, Am Hubland, 97074 Würzburg (Germany)
  2. Departamento de Quimica Fisica, Universidad Complutense, 28040 Madrid (Spain)
Publication Date:
OSTI Identifier:
22493438
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, 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