Internal energy distributions from nitrogen dioxide fluorescence. 3. Photolysis of jet-cooled N[sub 2]O[sub 4]

Journal Article · Thu Sep 30 04:00:00 EDT 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100141a006· OSTI ID:5525888

Sisk, W N; Miller, C E; Johnston, H S ^[1]

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1. Univ. of California, Berkeley, CA (United States) Lawrence Berkeley Lab., CA (United States)

A supersonic jet of N[sub 2]O[sub 4] is photolyzed at three wavelengths: 351, 248, and 193 nm. The resultant NO[sub 2] fluorescence is dispersed, the fluorescence spectrum is folded into a cumulative sum, and the internal energy distribution of almost nascent photolysis products is found by the method of article 1 of this series. The spread of these product internal energy distributions increases as the photolysis energy increases from 351 to 248 to 193 nm. The most probable internal energy increases between 351- and 248-nm photolysis, but at 193-nm photolysis it is about the same as, or somewhat lower than, that at 248 nm. This apparent anomaly is explained in terms of the electronic states of the products. The internal energy distribution derived from 351-nm data is examined by the method of prior distribution, and the photolysis products are found to be one NO[sub 2] molecule in the ground electronic state and the other in the [sup 2]B[sub t] electronic state with 3 or 4 quanta of bending vibration excitation. The internal energy distributions at 193 and 248 nm are combined with Kawasaki's time-of-flight translational energy distributions at 193 and 248 nm, and upon adding considerations of molecular orbitals the product states are assigned for photolysis at 193 and 248 nm. 31 refs., 14 figs., 2 tabs.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5525888
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:39; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
CHALCOGENIDES
CHEMICAL REACTIONS
COOLING
DECOMPOSITION
DISSOCIATION
EMISSION SPECTROSCOPY
ENERGY LEVELS
ENERGY TRANSFER
EXCITED STATES
FLUID FLOW
FLUORESCENCE
FLUORESCENCE SPECTROSCOPY
JETS
LEAST SQUARE FIT
LUMINESCENCE
MATRICES
MAXIMUM-LIKELIHOOD FIT
NITROGEN COMPOUNDS
NITROGEN DIOXIDE
NITROGEN OXIDES
NUMERICAL SOLUTION
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
SPECTROSCOPY
SUPERSONIC FLOW
TIME-OF-FLIGHT METHOD
VIBRATIONAL STATES