Competing dissociation channels in the photolysis of S[sub 2]Cl[sub 2] at 235 nm.

Autor: Einfeld, Tina S., Maul, Christof, Gericke, Karl-Heinz, Chichinin, Alexei
Předmět:
Zdroj: Journal of Chemical Physics; 9/1/2002, Vol. 117 Issue 9, p4214, 6p, 2 Diagrams, 1 Chart, 2 Graphs
Abstrakt: The photodissociation of disulfur dichloride (S[sub 2]Cl[sub 2]) at 235 nm has been studied by three-dimensional (3D) imaging of the chlorine product recoil in its ground state [sup 2]P[sub 3/2][Cl] and excited spin-orbit state [sup 2]p[sub 1/2][Cl[sup *]] employing the resonance enhanced multiphoton ionization and time-of-flight techniques. The photodissociation proceeds mainly along the three channels forming S[sub 2]+2C1 (1), S[sub 2]Cl+C1 (2), and 2 SC1 (3) photoproducts where slow and fast C1 fragments are released in (1) and (2), respectively. The relative yield of channel (1) with respect to channel (2) was determined to be 1.2:1.0. The yield of Cl[sup *], φ(Cl[sup *])=P(Cl[sup *])/[P(C1)+P(CI[sup *])], was found to be 0.35. The obtained state-specific velocity distributions of C1 and Cl[sup *] are mainly different in the high energy range: For Cl[sup *] the two dissociation channels are almost equally present, whereas in the case of ground state C1 the contribution of dissociation channel (2) is of minor importance. The dependence of the anisotropy parameter β on the fragment recoil velocity was directly determined due to the novel technique where the 3D momentum vector of a single reaction product is observed. For both spin-orbit states the anisotropy parameters differ for slow, intermediate, and fast chlorine atoms. The observed β values change from zero to slightly negative values up to positive values with increasing kinetic energy. These observations can be explained by two overlapping dissociation channels, where the two-body channel (2) releases the chlorine atom with high kinetic energy and a positive β parameter via an excited [sup 1]A state, whereas the three-body channel (1) proceeds mainly sequentially, where the first C1 atom is released with intermediate speed and a slightly negative β value via an excited [sup 1]B state, while the second C1 product atom in the decay of S[sub 2]C1 is released isotropically with slow... [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index