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research article

Dipole moments of HDO in highly excited vibrational states measured by Stark induced photofragment quantum beat spectroscopy

Theule, P  
•
Callegari, A  
•
Rizzo, Thomas R.  
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2005
The Journal of Chemical Physics

We report here a measurement of electric dipole moments in highly vibrationally excited HDO molecules. We use photofragment yield detected quantum beat spectroscopy to determine electric field induced splittings of the J=1 rotational levels of HDO excited with 4, 5, and 8 quanta of vibration in the OH stretching mode. The splittings allow us to deduce mu(a) and mu(b), the projections of dipole moment onto the molecular rotation inertial axes. We compare the measured HDO dipole moment components with the results of quantitative calculations based on Morse oscillator wave functions and an ab initio dipole moment surface. The vibrational dependence of the dipole moment components reflect both structural and electronic changes in HDO upon vibrational excitation; principally the vibrational dependence of the O-H bond length and bond angle, and the resulting change in orientation of the principal inertial coordinate system. The dipole moment data also provide a sensitive test of theoretical dipole moment and potential energy surfaces, particularly for molecular configurations far from equilibrium.

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Type
research article
DOI
10.1063/1.1864912
Web of Science ID

WOS:000228287900021

Author(s)
Theule, P  
Callegari, A  
Rizzo, Thomas R.  
Muenter, JS
Date Issued

2005

Published in
The Journal of Chemical Physics
Volume

122

Article Number

124312

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPM  
Available on Infoscience
December 15, 2005
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/221364
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