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The photodissociation of R-NO sub 2 molecules

Technical Report ·
OSTI ID:5325059

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