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Title: Communication: Creation of molecular vibrational motions via the rotation-vibration coupling

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.
Authors:
 [1] ;  [2] ;  [1]
  1. Department of Chemistry, Technical University of Denmark, Building 207, DK-2800 Kongens Lyngby (Denmark)
  2. (Australia)
Publication Date:
OSTI Identifier:
22415958
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 22; 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; ADIABATIC APPROXIMATION; BOND LENGTHS; CHEMICAL BONDS; COMPARATIVE EVALUATIONS; COUPLING; DEGREES OF FREEDOM; EXCITATION; HYDROFLUORIC ACID; LASER RADIATION; MOLECULES; ROTATION; TIME DEPENDENCE; WAVE PACKETS