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  4. Dipole Moment of Water in Highly Vibrationally Excited States: Analysis of Photofragment Quantum-Beat Spectroscopy Measurements Using a Local-Mode Hamiltonian
 
research article

Dipole Moment of Water in Highly Vibrationally Excited States: Analysis of Photofragment Quantum-Beat Spectroscopy Measurements Using a Local-Mode Hamiltonian

Theule, Patrice  
•
Muenter, John S.
•
Callegari, Andrea  
2009
The Journal of Physical Chemistry A

We present here the analysis of experimental Stark effect measurements made using photofragment quantum beat spectroscopy on the 14,0->, 15,0->, 18,0+> and 14,0-> 12 > vibrational states of H2O [Callegari, A.; et al. Science 2002, 297, 993.]. To link the measured Stark coefficients with the dipole surface, we analyze our results using a coupled anharmonic oscillator model, which takes into account the local-mode nature of higly excited OH stretching vibrations in water, and the tunneling between the two equivalent bonds. The large inertial frame tilt associated with the local-mode bond stretching results in a complex interaction between rotational-, vibrational-, and tunneling-motion, all of which become deeply entangled in the Stark coefficients. A perturbational approach makes it possible to analyze the problem at increasingly higher levels of approximation and to disentangle the different contributions, according to the different time scales involved. This simple model reproduces most experimental values to within a few percent, even for these highly vibrationally excited levels, and gives valuable insight into the complex rotational and vibrational motions that link the dipole moment surface with the Stark coefficients.

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Type
research article
DOI
10.1021/jp904035g
Web of Science ID

WOS:000271825800043

Author(s)
Theule, Patrice  
Muenter, John S.
Callegari, Andrea  
Date Issued

2009

Published in
The Journal of Physical Chemistry A
Volume

113

Start page

13418

End page

13427

Subjects

High-Resolution Spectrum

•

Band Intensities

•

Vapor

•

Absorption

•

H2O

•

Rotation

•

Photodissociation

•

Formaldehyde

•

Convergence

•

Energy

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPM  
Available on Infoscience
November 30, 2010
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/59635
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