Evidence for excited spin-orbit state reaction dynamics in F+H2: theory and experiment.

We describe fully quantum, time-independent scattering calculations of the F+H2-->HF+H reaction, concentrating on the HF product rotational distributions in v'=3. The calculations involved two new sets of ab initio potential energy surfaces, based on large basis set, multireference configuration-interaction calculations, which are further scaled to reproduce the experimental exoergicity of the reaction. In addition, the spin-orbit, Coriolis, and electrostatic couplings between the three quasidiabatic F+H2 electronic states are included.

Quantum-state resolved reaction dynamics at the gas-liquid interface: direct absorption detection of HF(v,J) product from F(2P)+squalane.

Exothermic reactive scattering of F atoms at the gas-liquid interface of a liquid hydrocarbon (squalane) surface has been studied under single collision conditions by shot noise limited high-resolution infrared absorption on the nascent HF(v,J) product. The nascent HF(v,J) vibrational distributions are inverted, indicating insufficient time for complete vibrational energy transfer into the surface liquid. The HF(v=2,J) rotational distributions are well fit with a two temperature Boltzmann analysis, with a near room temperature component (T(TD) approximately equal to 290 K) and a second much hotter scattering component (T(HDS) approximately equal to 1040 K).

Rotational Analysis of the 210 and 220 Bands of the ã 3B1 <-- &Xtilde; 1A1 System of Jet-Cooled Silicon Difluoride.

A combination least-squares and band contour analysis of the 2(1)0 and 2(2)0 bands of the laser-induced phosphorescence spectrum of the ã 3B1 <-- &Xtilde; 1A1 band system silicon difluoride, SiF2, has been completed. Spectra were taken under pyrolysis-jet conditions at a resolution of ca 0.04 cm-1.