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Photodissociation of NO/sub 2/-X (X = ClO, NO/sub 3/, Cl) molecules

Technical Report ·
OSTI ID:6504498

Studies of the photodissociation of NO/sub 2/-X molecules, where X = ClO, NO/sub 3/, and Cl, are reported here. Chlorine nitrate (ClONO/sub 2/) is photolyzed at 248 nm, and the product nitrate radical (NO/sub 3/) is detected by time-resolved resonance absorption. The sum of the primary and secondary NO/sub 3/ quantum yields is 1.7 +- 0.28(2sigma), as measured from analysis of the time-resolved absorption profile at NO/sub 3/ X(0,0,0,1). the Photolysis Induced Fluorescence (PIF) method, which represents the NO/sub 2/* emission spectrum as a linear combination of monoenergetically prepared NO/sub 2/ Laser Induced Fluorescence spectra, is derived. This method estimates the internal energy distribution (P(E/sub int/)) of NO/sub 2/* from photolysis over the range of observations, which is limited to the visible spectrum, from 400 to 800 nm or 25,000 to 12,500 cm/sup /minus/1/. The PIF spectra of nitrogen dioxide (N/sub 2/O/sub 5/) are studied at 248 and 193 nm. The PIF spectra of nitryl chloride (NO/sub 2/Cl) are studied at 266, 248 and 193 nm. This investigation demonstrates how the internal energy distribution of the reaction products changes with the energy of the photolysis laser. This study also demonstrates the change in the nascent P(E/sub int/) profile as the NO/sub 2/* molecule undergoes a controlled number of collisions. Time-of-Flight/Mass Spectrometry (TOF/MS) study of the photochemical reactions of NO/sub 2/Cl, performed in collaboration with Y.T. Lee group, is reported. This method gives the distribution of translational energies (P(E/sub Trans/)) of the product molecules, which is complimentary to the P(E/sub int/) from the PIF method. 74 refs., 101 figs., 22 tabs.

Research Organization:
Lawrence Berkeley Lab., CA (USA)
DOE Contract Number:
AC03-76SF00098
OSTI ID:
6504498
Report Number(s):
LBL-26462; ON: DE89007314
Country of Publication:
United States
Language:
English