Photodissociation dynamics of the A 2Sigma+ state of SH and SD radicals.

Atomic sulfur products from predissociation of the lowest rotational states of SH/SD A (2)Sigma(+) (v(')=0,1,2) are studied using velocity map imaging. The dissociation process, which is slow compared to rotation, is dominated by interference effects due to predissociation of states with low rotation quantum numbers prepared by photoexcitation using overlapping transitions of different parities. The measured product angular distributions can be modeled using the methods presented recently by Kim et al. [J. Chem. Phys. 125, 133316 (2006)]. The S((3)P(J)) (2+1) resonance enhanced multiphoton ionization scheme used in the detection step of the experiment is sensitive to the angular momentum polarization of the atomic fragments. S((3)P(J)), J=2,1,0, fine-structure yields, angular distributions, and atom polarization parameters are reported. Strong polarization of the S((3)P(2,1)) products was observed along with a weak sensitivity of the branching ratio to excess energy and a full insensitivity of the atomic product polarization to excess energy. None of the data fit the predictions of either adiabatic or diabatic photodissociation, emphasizing the need for a fully quantum treatment.

Photofragment alignment in the photodissociation of I2 from 450 to 510 nm.

A combination of velocity map imaging and slicing techniques have been used to measure the product recoil anisotropy and angular momentum polarization for the photodissociation process I2-->I(2P(3/2))+I(2P(3/2)) and I2-->I(2P(3/2)))+I(2P(1/2)) in the 450-510 nm laser wavelength region using linearly polarized photolysis and probe laser light. The former channel is produced predominantly via perpendicular excitation to the 1Piu state, and the latter is predominantly parallel, via the B 3Pi(0u)+ state. In both cases we observe mostly adiabatic dissociation, which produces electronically aligned iodine atoms in the mid /m/=1/2 states with respect to the recoil direction.