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

Journal Article · Tue Jul 28 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4927396· OSTI ID:22493438

Albert, Julian; Falge, Mirjam; Hildenbrand, Heiko; Engel, Volker ^[1]; Gomez, Sandra; Sola, Ignacio R. ^[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)

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, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 143; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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