INTERNAL STATE DISTRIBUTIONS OF PRODUCT OH AND NO FROM PHOTODISSOCIATION OF NITRIC ACID AT 193 NM.

G. H. LEU, I. C. CHEN, Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan, ROC 30043.

The distributions of vibrational, rotational, spin-orbit and lambda -doublet states of nascent NO and OH are obtained using the A-X transition of both OH and NO via the technique of laser-induced fluorescence. NO is produced from the secondary dissociation of fragment NO2 from nitric acid after photolysis at 193 nm. About 3% of available energy is distributed to rotation of OH fragment; no vibrational excited OH was observed. It was found that about 87.7% of excess energy to be directed to the internal energy of fragment NO2. According to the measurement of internal state distributions of secondary product NO, the partition of energy in NO X2Pi is calculated to be ~840 cm-1 in vibration and ~ 1410 cm-1 in rotation. The spin-obit state 2Pi1/2 of NO is populated about twice of that in 2Pi3/2 for the vibrational levels v=0,1,2. The measured populations of vibrational states v=0,1,2 are 0.75, 0.19 and 0.07, respectively ; these populations agree with result calculated with the statistical model, prior theory. The experimental data indicate that although NO2 photochemical from nitric acid , was proposed to be in an electronically excited state, the state distribution of NO from unstable NO2 agree with those from NO2 excited with monochromatic light in the UV-vis range after average for the broad distribution of internal energy. Hence this unknown electronic state of NO2 is expected to be coupled to the ground electronic surface then leading to dissociation.