Js. Spasov et Ji. Cline, Scalar and angular correlations in CF3NO photodissociation: Statistical and nonstatistical channels, J CHEM PHYS, 110(19), 1999, pp. 9568-9577
Polarized 1+1' REMPI combined with TOFMS detection was used to obtain recoi
l speed distributions, NO product rotational distributions, and mu-v-j(NO)
angular correlations in the photofragmentation of CF3NO between 585 and 650
nm. At wavelengths longer than 610 nm dissociation occurs only on the S-0
potential energy surface of CF3 NO. At 585 nm the product recoil speed dist
ribution is bimodal, with the higher speed component attributed to dissocia
tion across a potential barrier on the T-1 surface. Measurements of the T-1
channel NO product trajectory show it has no laboratory frame rotational a
lignment or recoil anisotropy, but has a significant preference for v perpe
ndicular to j(NO) angular correlation, reaching a maximal value of beta(0)(
0)(22) =-0.308+/-0.052. The results are interpreted using the results of st
atistical phase space theory and classical trajectory calculations. It is c
oncluded that S-0 channel dissociation occurs by a statistical dissociation
mechanism whereas the T-1 channel dynamics is dominated by exit channel re
coil forces due to a potential barrier. (C) 1999 American Institute of Phys
ics. [S0021-9606(99)00719-9].