The photodissociation of R-NO sub 2 molecules
The internal energy distributions, P(E{sub int}), are derived for rovibronically excited NO{sub 2} ensembles and the chemiluminescent NO + O {yields} NO{sub 2}* reaction. The P(E{sub int}) distribution is evaluated using the Integrated Fluorescence (IF) method. The performance of the IF model was assessed using measurements of the NO{sub 2}* spectral distribution from the NO + O {yields} NO{sub 2}* reaction. The results show that the NO{sub 2}* P(E{sub int}) distribution is sharply peaked at 25,130 cm{sup {minus}1}. Photodissociation of nitromethane between 193.3nm and 248.5nm demonstrates that the NO{sub 2}* P(E{sub int}) transform from inverted distributions sharply peaked at 25,130 cm{sup {minus}1} to ones in which a majority of the NO{sub 2}* components have internal energies less than 15,000 cm{sup {minus}1}. The wavelength dependence of HONO{sub 2} and CINO{sub 2} photodissociations was investigated in greater detail. The transformations in the NO{sub 2}* P(E{sub int}) contours are linked to changes in which potential energy surface dominates the dissociation dynamics. The principal differences between CINO{sub 2} and HONO{sub 2} photodissociations are explained in terms of the perturbations induced by the R group on the local C{sub 2v} symmetry of the NO{sub 2} chromophore. 69 refs., 129 figs., 51 tabs.
- Research Organization:
- Lawrence Berkeley Lab., CA (United States)
- Sponsoring Organization:
- DOE; USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5325059
- Report Number(s):
- LBL-30540; ON: DE91016992
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201 -- Chemical & Physicochemical Properties
400500* -- Photochemistry
CHEMICAL EXPLOSIVES
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
DATA
DATA ACQUISITION SYSTEMS
DATA ANALYSIS
DECOMPOSITION
DISSOCIATION
EMISSION SPECTRA
EMISSION SPECTROSCOPY
ENERGY-LEVEL TRANSITIONS
EXCIMER LASERS
EXPERIMENTAL DATA
EXPLOSIVES
FLUORESCENCE SPECTROSCOPY
FUNCTIONS
GAS LASERS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
LASERS
MATHEMATICAL MODELS
NITRIC ACID
NITRO COMPOUNDS
NITROGEN CHLORIDES
NITROGEN COMPOUNDS
NITROMETHANE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
RESEARCH PROGRAMS
SPECTRA
SPECTROSCOPY
TESTING
THEORETICAL DATA
VALIDATION
WEIGHTING FUNCTIONS