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research article

Local modes of HOOH probed by optical‐infrared double resonance

FLEMING, PR
•
LI, MY
•
RIZZO, TR  
1991
The Journal of Chemical Physics

We have used an optical-infrared double resonance technique to probe the nature of the eigenstates prepared by 4-nu-OH vibrational overtone excitation in hydrogen peroxide. A visible dye laser excites the 4 <-- 0 OH stretch transition and an optical parametric oscillator promotes the molecules above the dissociation threshold by a DELTA-upsilon-OH = 2 transition from the 4-nu-OH level. Fixing the overtone excitation laser wavelength and scanning the wavelength of the infrared photon while monitoring the dissociation fragments by laser-induced fluorescence generates an infrared predissociation spectrum of the vibrationally excited molecule that contains information about vibrational state mixing at the 4-nu-OH level. This spectrum indicates that the zeroth-order state that gives oscillator strength to the 4 <-- 0 OH stretch transition (i.e., the 4-nu-OH bright state) is almost entirely comprised of a single vibrational eigenstate. Since the bright state is predominantly an OH stretch, the vibrational eigenstate prepared by 4-nu-OH vibrational overtone excitation is well localized on the OH bond. This localization allows us to perform sequential local mode-local mode excitation of the two equivalent OH oscillators in HOOH.

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Type
research article
DOI
10.1063/1.461094
Author(s)
FLEMING, PR
LI, MY
RIZZO, TR  
Date Issued

1991

Published in
The Journal of Chemical Physics
Volume

95

Issue

2

Start page

865

End page

871

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/20.500.14299/221319
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