Site and Isotopic Effects on the Angular Anisotropy of Products in the Photodissociation of Ethene at 157 nm

We measured angular-anisotropy parameters beta(E(t)) of fragments from photolysis of ethene and four isotopic variants at 157 nm using photo-fragment translational spectroscopy and selective photoionization. The averaged beta value of products ranges from -0.17 to 0.10, depending on dissociation pathways. Angular distributions of atomic hydrogen produced from C(2)H(4) and C(2)D(4) are isotropic. For dissociation into C(2)H(2) + H(2), beta has a small negative value whereas dissociation into C(2)D(2) + D(2) has an isotropic angular distribution. The photolysis of dideuterated ethene reveals site and isotopic effects on the angular distributions of products; products H(2), HD, and D(2) from photolysis of 1,1-CH(2)CD(2) have negative, nearly zero, and positive values of beta, respectively. Molecular hydrogen from photolysis of 1,2-cis-CHDCHD has a negative beta value and the anisotropy has a trend D(2) > H(2) > HD. Photolysis of 1,2-trans-CHDCDH produced a result similar to photolysis of 1,2-cis-CHDCHD for the angular anisotropy of molecular hydrogen except slightly more isotropic. A calculation of optimized geometries of ethene in the ground electronic state and pertinent transition structures enables a qualitative interpretation of the site and isotopic effects on the angular anisotropy of products. We deduce that the photoexcited state of ethene at 157 nm has a major character (1)B(1u) that produces a transition dipolar moment parallel to the C=C bond.