Application of Transition State Theory to Estimate Diffusion Controlled Bimolecular Reaction Rate Constants.
نویسندگان
چکیده
منابع مشابه
Activated diffusion of benzene in NaY zeolite: Rate constants from transition state theory with dynamical corrections
We calculated transition state theory and exact rate coefficients for benzene jumps in Na-Y zeolite between 150 and 500 K. This is the first exact flux correlation function rate calculation for a non-spherical molecule inside a zeolite. We calculated rates for jumps between SII and W sites, located near Na ions in 6-rings and in 12-rings windows, respectively. Partition function ratios were cal...
متن کاملRate constants from the reaction path Hamiltonian. II. Nonseparable semiclassical transition state theory.
For proton transfer reactions, the tunneling contributions to the rates are often much larger than thermally activated rates at temperatures of interest. A number of separable tunneling corrections have been proposed that capture the dependence of tunneling rates on barrier height and imaginary frequency size. However, the effects of reaction pathway curvature and barrier anharmonicity are more...
متن کاملRelation between State-Selected or State-Averaged Cross Sections of Endothermic Reactions and Rate Constants of Exothermic Reactions. Application of Bimolecular Microcanonical Activated Complex Theory*
INTRODUCTION In a previous paper1 a microcanonical ensemble of reacting pairs of molecules in bimolecular reactions was considered and a quasiequilibrium assumed between the pairs and activated complexes moving in a positive direction along the reaction coordinate. As noted previously, this microcanonical version of activated complex theory is related to the usual version by means of a Laplace ...
متن کاملSurface hopping, transition state theory, and decoherence. II. Thermal rate constants and detailed balance.
We investigate a simple approach to compute a non-adiabatic thermal rate constant using the fewest switches surface hopping (FSSH) dynamics. We study the effects of both decoherence (using our augmented-FSSH (A-FSSH) algorithm) and forbidden hops over a large range of parameters, including high and low friction regimes, and weak and strong electronic coupling regimes. Furthermore, when possible...
متن کاملEfficient dynamical correction of the transition state theory rate estimate for a flat energy barrier.
The recrossing correction to the transition state theory estimate of a thermal rate can be difficult to calculate when the energy barrier is flat. This problem arises, for example, in polymer escape if the polymer is long enough to stretch between the initial and final state energy wells while the polymer beads undergo diffusive motion back and forth over the barrier. We present an efficient me...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Acta Chemica Scandinavica
سال: 1981
ISSN: 0904-213X
DOI: 10.3891/acta.chem.scand.35b-0529