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...

The reaction of atomic boron, B(2P), with the simplest alkene, C2H4, has been investigated under single collision conditions in crossed beam experiments with mass spectrometric detection. Our experimental data clearly showed that the atomic boron versus hydrogen exchange reaction led to molecule(s) of gross formula C2H3B via bound intermediate(s). According to the experimentally derived fractio...

The Whitten-Rabinovitch (WR) approximation used in the semi-classical calculation of the Rice-Ramsperger-Kassel-Marcus (RRKM) unimolecular reaction rate constant was improved for reliable application to protein reactions. The state sum data for the 10-mer of each amino acid calculated by the accurate Beyer-Swinehart (BS) algorithm were used to obtain the residue-specific correction functions (w...