Overtone spectroscopy of the hydroxyl stretch vibration in hydroxylamine (NH[sub 2]OH)
- Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States)
We present photoacoustic spectra of the second (3[nu][sub OH]), third (4[nu][sub OH]), and fourth (5[nu][sub OH]) overtone bands of the hydroxyl stretch vibration in hydroxylamine. Asymmetric rotor simulations of the rovibrational contours provide rotational constants and an estimate of the homogeneous linewidth. The fourth overtone band appears anomalously broad relative to the two lower bands, reflecting a sharp increase in the rate of intramolecular vibrational energy redistribution (IVR). By contrast, the calculated density of states increases smoothly with energy. The homogeneous linewidth of the fourth overtone transition is similar to that measured by Luo [ital et] [ital al]. [J. Chem. Phys. [bold 93], 9194 (1990)] for the predissociative sixth overtone band, supporting the conclusion that the broadening arises from increased (ro)vibrational coupling at an energy between the third and fourth overtone states.
- OSTI ID:
- 7079586
- Journal Information:
- Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 102:2; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
664400 -- Experimentally Derived Information on Atomic & Molecular Properties-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
AMINES
ASYMMETRY
CATALYSIS
CHEMICAL REACTIONS
CHEMISTRY
COLLISIONS
COUPLING
DECOMPOSITION
DISSOCIATION
ELONGATION
ENERGY LEVELS
ENERGY-LEVEL DENSITY
EXCITED STATES
HARMONICS
HYDROXYL RADICALS
HYDROXYLAMINE
INTERATOMIC FORCES
LINE WIDTHS
MOLECULE COLLISIONS
MOLECULE-MOLECULE COLLISIONS
ORGANIC COMPOUNDS
OSCILLATIONS
PHOTOACOUSTIC SPECTROSCOPY
PHOTOCHEMISTRY
PREDISSOCIATION
RADICALS
ROTORS
SIMULATION
SPECTROSCOPY
SURFACES
VIBRATIONAL STATES