Vibrational overtone spectroscopy of the 4. nu. sub OH +. nu. sub OH prime combination level of HOOH via sequential local mode--local mode excitation

Journal Article · Wed Apr 15 04:00:00 EDT 1992 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.462665· OSTI ID:7234494

Luo, X; Fleming, P R; Rizzo, T R ^[1]

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1. Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)

Sequential pumping of the local OH stretch vibrations in hydrogen peroxide using infrared-optical double resonance permits spectroscopic access to the 4{nu}{sub OH}+{nu}{sub OH{prime}} combination level. Analysis of the rotationally resolved vibrational overtone spectra generated by this technique determines approximate rotational constants for this level and a value of 17 051.8{plus minus}3.4 cm{sup {minus}1} for the O--O bond dissociation energy. The linewidths of individual zeroth-order rotational transitions increase sharply with increasing {ital K} and change from smooth Lorentzian profiles to clumps of individual lines. The {ital K} dependence of the clump widths suggests that an {ital a}-axis Coriolis interaction is the primary coupling mechanism between the zeroth-order bright state and dark bath states. As a function of increasing {ital J}, each clump coalesces into a smooth Lorentzian profile. We interpret this {ital J} dependence in terms of a model that includes rotationally induced vibrational coupling among zeroth-order dark states.

• OSTI ID: 7234494
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 96:8; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664200* -- Spectra of Atoms & Molecules & their Interactions with Photons-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
CORIOLIS FORCE
DISSOCIATION ENERGY
DOUBLE RESONANCE METHODS
ENERGY
ENERGY LEVELS
EXCITED STATES
HARMONICS
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
HYDROXYL RADICALS
LINE WIDTHS
OSCILLATIONS
OXYGEN COMPOUNDS
PEROXIDES
RADICALS
RESOLUTION
ROTATIONAL STATES
VIBRATIONAL STATES