Stuart J. Greaves

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Transient, broadband infra-red absorption spectroscopy with picosecond time resolution has been used to study the dynamics of reactions of CN radicals with tetrahydrofuran (THF) and d(8)-THF in liquid solutions ranging from neat THF to 0.5 M THF in chlorinated solvents (CDCl(3) and CD(2)Cl(2)). HCN and DCN products were monitored via their v(1) (C≡N(More)
The dynamics of reactions of CN radicals with cyclohexane, d(12)-cyclohexane, and tetramethylsilane have been studied in solutions of chloroform, dichloromethane, and the deuterated variants of these solvents using ultraviolet photolysis of ICN to initiate a reaction. The H(D)-atom abstraction reactions produce HCN (DCN) that is probed in absorption with(More)
Solvent-solute interactions influence the mechanisms of chemical reactions in solution, but the response of the solvent is often slower than the reactive event. Here, we report that exothermic reactions of fluorine (F) atoms in d3-acetonitrile and d2-dichloromethane involve efficient energy flow to vibrational motion of the deuterium fluoride (DF) product(More)
Solvent collisions can often mask initial disposition of energy to the products of solution-phase chemical reactions. Here, we show with transient infrared absorption spectra obtained with picosecond time resolution that the nascent HCN products of reaction of CN radicals with cyclohexane in chlorinated organic solvents exhibit preferential excitation of(More)
Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands:(More)
Transient electronic absorption measurements with 1 ps time resolution follow XeF2 photoproducts in acetonitrile and chlorinated solvents. Ultraviolet light near 266 nm promptly breaks one Xe-F bond, and probe light covering 320-700 nm monitors the products. Some of the cleaved F atoms remain in close proximity to an XeF fragment and perturb the electronic(More)
Vibrationally inelastic scattering is a fundamental collision process that converts some of the kinetic energy of the colliding partners into vibrational excitation(,). The conventional wisdom is that collisions with high impact parameters (where the partners only 'graze' each other) are forward scattered and essentially elastic, whereas collisions with low(More)
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