We consider the bimolecular formation and redissociation of complexes using classical trajectories and the survival probability distribution function P(E,J,t) of the intermediate complexes at time t as a function of the energy E and total angular momentum quantum number J. The P(E,J,t) and its deviation from single exponential behavior is a main focus of the present set of studies. Together wit...

Experimental observations of D fragments from the predissociation of rovibrationally excited partially deuterated 2-hydroxyethyl radicals, CD(2)CD(2)OH, are reported, and possible dissociation channels are analyzed by theory. The radicals are produced by photolysis of 2-bromoethanol at 202-215 nm, and some of them have sufficient internal energy to predissociate. D fragments are detected by 1 +...

Using the potential surface information for (KCl)5 and Ar9 and partition function models introduced in the preceding paper @Ball and Berry, J. Chem. Phys. 109, 8541 ~1998!# we construct a stochastic master equation for each system using Rice–Ramsperger–Kassel–Marcus ~RRKM! theory for transition rates between adjacent minima. We test several model approximations to reactant and transition-state ...

Time resolved studies of silylene, SiH2, generated by the 193 nm laser flash photolysis of phenylsilane, have been carried out to obtain rate coefficients for its bimolecular reactions with methyl-, dimethyl- and trimethyl-silanes in the gas phase. The reactions were studied over the pressure range 3-100 Torr with SF6 as bath gas and at five temperatures in the range 300-625 K. Only slight pres...

β-Hydroxyperoxyl radicals are formed during atmospheric oxidation of unsaturated volatile organic compounds such as isoprene. They are intermediates in the combustion of alcohols. In these environments the unimolecular isomerization and decomposition of β-hydroxyperoxyl radicals may be of importance, either through chemical or thermal activation. We have used ion-trap mass spectrometry to gener...

Ab initio calculations at the G3 level were used in a theoretical description of the kinetics and mechanism of the chlorine abstraction reactions from mono-, di-, tri- and tetra-chloromethane by chlorine atoms. The calculated profiles of the potential energy surface of the reaction systems show that the mechanism of the studied reactions is complex and the Cl-abstraction proceeds via the format...

The dissociation of pentane-2,4-dione radical cation has been studied by ab initio direct classical trajectory calculations at the MP2/6-31G(d) level of theory. A bond additivity correction has been used to improve the MP2 potential energy surface (BAC-MP2). A microcanonical ensemble was constructed using quasiclassical normal-mode sampling by distributing 10 kcal/mol of excess energy above ZPE...