A detailed comparison between the dynamics of photodissociation of (CH 3)3CONO from its first two excited singlet states is presented. The fragmentation processes are studied by exciting the molecule at 365.8 and 351.8 nm [S1(nπ*) ← S0 transition] and at 250 nm [S2(ππ*) ← S0 transition] and probing the NO fragment by single photon laser induced fluorescence combined with polarization and sub-Doppler spectroscopy. The μ, v, and J vector correlations, Λ-doublet and spin-orbit populations, and the vibrational, rotational, and translational energy content of the NO fragment are determined. The scalar and vectorial properties point on different mechanisms of fragmentation from the S1 and S2 states, but both are highly selective. The findings of this study, especially those concerning the less studied S2 state, can be utilized to predict the behavior of other alkyl nitrites and demonstrate the power of the techniques mentioned above in characterizing the dynamics of photodissociation, even for large molecules.
|Number of pages||9|
|Journal||Journal of Chemical Physics|
|State||Published - 1 Jan 1988|
ASJC Scopus subject areas
- Physics and Astronomy (all)
- Physical and Theoretical Chemistry