Gas-phase OH-oxidation of 2-butanethiol: Multiconformer transition state theory rate constant with constrained transition state randomization
Luı́s P. Viegas
Abstract
The prediction of transition state (TS) geometries is crucial for the discovery of reaction mechanisms and calculation of accurate rate constants via TS theory (TST). The existence of a multitude of TS conformers requires the use of adaptations to conventional TST such as multiconformer TST (MC-TST), where considerable computational effort is spent performing the TS sampling. Here, we calculate the MC-TST high-pressure limit rate constant for the 2-butanethiol + OH reaction by including a constrained TS randomization procedure, which yields a rate constant in good agreement with experimental work and is easily adaptable to other OH-oxidation reactions.
Topics & Concepts
Transition state theoryReaction rate constantChemistryThermodynamicsConstant (computer programming)Limit (mathematics)State (computer science)Work (physics)Gas phasePhysical chemistryComputational chemistryPhysicsKineticsMathematicsQuantum mechanicsMathematical analysisAlgorithmComputer scienceProgramming languageAdvanced Chemical Physics StudiesSpectroscopy and Quantum Chemical StudiesCatalysis and Oxidation Reactions