Near-ultraviolet photodissociation of thiophenol.

H(D) Rydberg atom photofragment translational spectroscopy has been used to investigate the dynamics of H(D) atom loss C6H5SH(C6H5SD) following excitation at many wavelengths lambda phot in the range of 225-290 nm. The C6H5S cofragments are formed in both their ground (X(2)B1) and first excited ((2)B2) electronic states, in a distribution of vibrational levels that spreads and shifts to higher internal energies as lambda(phot) is reduced. Excitation at lambda(phot) > 275 nm populates levels of the first (1)pi pi* state, which decay by tunnelling to the dissociative (1)pi sigma* state potential energy surface (PES). S-H torsional motion is identified as a coupling mode facilitating population transfer at the conical intersection (CI) between the diabatic (1)pi pi* and (1)pi sigma* PESs. At shorter lambda(phot), the (1)pi sigma* state is deduced to be populated either directly or by efficient vibronic coupling from higher (1)pipi* states. Flux evolving on the (1)pi sigma* PES samples a second CI, at longer R(S-H), between the diabatic (1)pi sigma* and ground ((1)pi pi) PESs, where the electronic branching between ground and excited state C6H5S fragments is determined. The C6H5S(X(2)B1) and C6H5S((2)B2) products are deduced to be formed in levels with, respectively, a' and a'' vibrational symmetry-behavior that reflects both Franck-Condon effects (both in the initial photoexcitation step and in the subsequent in-plane forces acting during dissociation) and the effects of the out-of-plane coupling mode(s), nu11 and nu16a, at the (1)pi sigma*/(1)pi pi CI. The vibrational state assignments enabled by the high-energy resolution of the present data allow new and improved estimations of the bond dissociation energies, D0(C6H5S-H) < or = 28,030 +/- 100 cm(-1) and D0(C6H5S-D) < or = 28,610 +/- 100 cm(-1), and of the energy separation between the X(2)B1 and (2)B2 states of the C6H5S radical, T(00) = 2800 +/- 40 cm(-1). Similarities, and differences, between the measured energy disposals accompanying UV photoinduced X-H (X = S, O) bond fission in thiophenol and phenol are discussed.