reaction kinetics theory/ RRKM theoryunimolecular reactionseffective strong collision frequencyrelaxation rateinternal energyergodic collision theoryIt is proposed that the accuracy of the RRKM theory can be improved by replacing the usual collision frequency by an effective collision frequency defi...
The microsopic rate constants of N( 4S)+CH 2X(X=F,Cl) reaction have been calculated by RRKM theory. The barrierless dissociation was handled with the loosing transition state model. The results reveal that when activated internal energy is low (280.29 kJ/mol), the major products of N( 4S...
Collision complex model for spin forbidden reactions: Quenching of O(1D) by N2 A collision complex model based on the RRKM theory of unimolecular decomposition is developed to describe spin‐forbidden molecular collision processes. Th... Tully,C John - 《Journal of Chemical Physics》 被引量: 226...
Unimolecular rate theory for various types of reactions is implemented for any looseness of transition state. Quantum states are counted for all but the “transitional” modes, their phase space being counted via Monte Carlo sampling. The rate constant kEJ is then weighted with the initial E and...
Unimolecular reactions of chemically activated CF2BrCF2CH3 and CF2BrCF2CD3: evidence for 1,2-FBr interchange The CF3CFBrCH3 (CD3) molecules rapidly, relative to the reverse reaction, eliminate HBr or DBr to give the observed product CF3CF=CH2 (CD2). ... CE Lisowski,JR Duncan,GL Heard,...
The kinetics and mechanisms for SiH2 + Si2H6 and SiH3 + Si2H5 reactions and the related unimolecular decomposition of Si3H8 have been investigated by ab initio molecular orbital theory based on the QCISD(T)/CBS//QCISD/6-311++G(d,p) metho... P Raghunath,MC Lin - 《Journal of Physical...
The OH(X2Π, υ = 0) rotational energy distribution in the reaction of O(1D) + H2 The rotational energy distribution of OH(υ=0) from the reaction O( 1D) + H 2 OH(X 2Π. υ. J) + Π has been determined and found to be close to distributions predicted by information theory an...
The unimolecular reaction mechanism of the CH2XCHFO (X = H, F) radicals was studied using the ab initio G2(MP2, SVP) theory. Three kinds of reaction pathways, namely bond scission, three-center elimination of HF and isomerization, were examined. Both the energy-specific rate constant [k(...
Rice–Ramsperger–Kassel–Marcus theory.Anharmonic and harmonic rate constants were calculated in the unimolecular reaction HCO2 → H + CO2 with Yao and Lin (YL) method. In microcanonical case, the total number of states and density of states increase reasonably with the increasing of the total...
On the application of RRKM theory to the unimolecular isomerization of monofluorocyclopropane: a reaction with multiple fall-off characteristics?Monofluorocyclopropane isomerizes at 475 掳C to form cis- and trans-1-fluoropropene, 2-fluoropropene, and 3-fluoropropene. The relative amounts of these...