Rsc_cp_c0cp02671a 1..11

In this paper we report slice imaging polarization experiments on the state-to-state photodissociation at 42 594 cm 1 of spatially oriented OCS(v2 = 1|JlM = 111) CO(J) + S(D2). Slice images were measured of the three-dimensional recoil distribution of the S(D2) photofragment for different polarization geometries of the photolysis and probe laser. The high resolution slice images show well separated velocity rings in the S(D2) velocity distribution. The velocity rings of the S(D2) photofragment correlate with individual rotational states of the CO(J) cofragment in the JCO = 57–65 region. The angular distribution of the S( D2) velocity rings are extracted and analyzed using two different polarization models. The first model assumes the nonaxial dynamics evolves after excitation to a single potential energy surface of an oriented OCS(v2 = 1|JlM = 111) molecule. The second model assumes the excitation is to two potential energy surfaces, and the OCS molecule is randomly oriented. In the high J region (JCO = 62–65) it appears that both models fit the polarization very well, in the region JCO = 57–61 both models seem to fit the data less well. From the molecular frame alignment moments the m-state distribution of S(D2) is calculated as a function of the CO(J) channel. A comparison is made with the theoretical m-state distribution calculated from the long-range electrostatic dipole–dipole plus quadrupole interaction model. The S(D2) photofragment velocity distribution shows a very pronounced strong peak for S(D2) fragments born in coincidence with CO(J = 61).