The bond dissociation kinetics of tethered atomic (Morse potential) chains under tensile stress is studied. Both RRKM (fully anharmonic, Monte Carlo) and RRK (harmonic appproximation) theory are applied to predict bond dissociation rate constants as a function of energy and tensile force. For chains with N P 3 atoms a hybrid statistical theory is used involving a harmonic approximation for moti...

A theory that describes the non-RRKM (non-Rice-Ramsperger-Kassel-Marcus) effects in the lifetime statistics of activated ozone molecules is derived. The non-RRKM effects are shown to originate due to the diffusive energy exchange between vibrational and rotational degrees of freedom in ozone molecule. The lifetime statistics is found to be intramolecular diffusion controlled at long times. The ...

We consider for bimolecular recombination reactions the K-adiabatic versus the K-active forms of RRKM theory, where K is the component of the total angular momentum along the axis of least moment of inertia of the recombination product. When that product is approximately a prolate symmetric top, with two moments of inertia of the product substantially larger than the third, K becomes a dynamica...

The methyl (•CH3) + 3O2 radical is an important reaction in both atmospheric and combustion processes. We investigated potential energy surfaces for the effect of CO2 H2O molecules on a •CH3+ O2 system. mechanism three systems, i.e., •CH3 3O2, (+CO2) (+H2O), were explored using ab initio/DFT methods [CCSD(T)//M062X/6-311++G(3df,3pd)] combination with Rice−Ramsperger−Kassel−Marcus (RRKM)/master-...

In the pioneering work by R. A. Marcus, solvation effect on electron transfer (ET) processes was investigated, giving rise to celebrated nonadiabatic ET rate formula. this work, basis of thermodynamic potentials analysis, we reexamine Marcus' formula with respect Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Interestingly, obtained RRKM analogue, which recovers original that is in a linear scena...

The Rice–Ramsperger–Kassel–Marcus (RRKM) theory provides a simple yet powerful rate for calculating microcanonical constants. In particular, it has found widespread use in combination w...