Photodissociation of Cl2SO at 248 and 193 nm in a molecular beam

A pulse molecular beam of Cl₂SO was photodissociated at 248 and 193 nm. The time-of-flight distributions were observed for the photofragments, Cl, ClSO and SO. The primary processes are Cl + ClSO (I), 2Cl + SO (II) and Cl₂ + SO (III). At 193 nm the measured translational energy distributions imply a vibrationally excited ClSO fragment in process (I), and a simultaneous dissociation in process (II). The relative quantum yield is φ_I < φ_II. At 248 nm a radical process (I) is dominant compared to a molecular process (III).     

On the path integral representation of stochastic processes

We derive the path integral representation of the conditional probability for a Markovian process starting from the master equation. Existing derivations require both the variable and the transition probability to be extensive. We show that this requirement may be relaxed if Langer's formula for the transition probability is used. We prove that different path integral representations appearing in the literature are in fact equivalent and correspond to various choices of an arbitrary parameter.This work was supported in part by the National Science Foundation and the Office of Naval Research (Project SQUID).     

Synthetic procedure for various selenium-containing electron donors of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) type

Six selenium variants of BEDT-TTF have been successfully synthesized by a newly developed synthetic method that involves a combination of two key reactions for the construction of two kinds of heterocyclic rings: the first is a one-pot formation of 1,3-dichalcogenole-2-chalcogenones from a common starting material, THP-protected 2-(ethynylthio)ethanol, leading to the inner five-membered rings, and the other is the annelation of the outer six-membered heterocyclic ring onto the inner ring by an intramolecular transalkylation reaction on a chalcogen atom. This method turned out to be widely applicable to the syntheses of the electron donors of bis(ethylenedithio)- and bis(ethyleneselenothio)-substituted types. However, synthetic attempts to form analogous donors of the bis(ethylenediseleno)-substituted type from THP-protected 2-(ethynylseleno)ethanol were unsuccessful. This is attributable to the predominance of side-reactions via a seleniranium (episelenonium) salt over the desired six-membered ring formation by transalkylation via a seleninium salt.