Communication: Creation of molecular vibrational motions via the rotation-vibration coupling
- Department of Chemistry, Technical University of Denmark, Building 207, DK-2800 Kongens Lyngby (Denmark)
Building on recent advances in the rotational excitation of molecules, we show how the effect of rotation-vibration coupling can be switched on in a controlled manner and how this coupling unfolds in real time after a pure rotational excitation. We present the first examination of the vibrational motions which can be induced via the rotation-vibration coupling after a pulsed rotational excitation. A time-dependent quantum wave packet calculation for the HF molecule shows how a slow (compared to the vibrational period) rotational excitation leads to a smooth increase in the average bond length whereas a fast rotational excitation leads to a non-stationary vibrational motion. As a result, under field-free postpulse conditions, either a stretched stationary bond or a vibrating bond can be created due to the coupling between the rotational and vibrational degrees of freedom. The latter corresponds to a laser-induced breakdown of the adiabatic approximation for rotation-vibration coupling.
- OSTI ID:
- 22415958
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion
State resolved photodissociation of vibrationally excited water: Rotations, stretching vibrations, and relative cross sections