Abstract
CF3I is photodissociated in a molecular beam with 248 nm laser lighl. Fragmentation takes place into CF3 and I(2P3/2) or I(2P1/2). The quantum yield for excited I (I* = I(2P1/2)) formation is determined to be 0.92. The CF3 fragments are found to be considerably vibrationally excited. Of the available energy in the CF3 + I* channel 39% (0.69 eV) appears on the average as vibrational energy in the CF3 radical. The angular distributions in both channels show predominantly parallel character. It can be concluded that at this wavelength 97% of the total absorption is due to the 3Q0 ← 1A1 transition and only 3% to the 1Q ← 1A1 transition. Most of the signal in the CF3 + I channel originates from an effective crossing between the 3Q0 and 1Q states. A coupled channel calculation is performed to obtain a better insight into the dissociation dynamics of the CF3I molecule. The results indicate that the CF3 fragments from dissociation of CF3I at 248 nm may be expected to be vibrationally excited. However, the experimental distribution has a higher average energy and is much broader. An explanation for this phenomenon is suggested.
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