A Full Dimensional Quasiclassical Trajectory Study of Cl + CH₄ Rate Coefficients

Abstract

The Cl + CH4 reaction has been investigated using a full dimensional quasiclassical trajectory technique and a new potential energy surface. The new surface is generated by expanding the interaction in terms of minimum energy paths in the Bond Order space. Results are compared with those obtained on another recently proposed potential energy surface and with experimental data.

Quasiclassical trajectory study of the SiH4+H→SiH3+H2 reaction on a global ab initio potential energy surface

“…In fact, the QCT method has been widely used to study all kinds of dynamical problems for reaction systems involving three and four atoms [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43] over the decades and is becoming popular in studying the reaction dynamics of larger systems. [44][45][46][47][48][49] In the present work, we performed detailed QCT calculations on the 12-dimensional ab initio WSB surface 22 for the SiH 4 +H→ SiH 3 +H 2 reaction. Various dynamical quantities are obtained and reaction mechanisms are analyzed.…”

Crossed‐Beam and Quantum Dynamics Studies of the Reaction Cl + CHD3

“…There have been numerous theoretical studies of the Cl + CH 4 reaction and its reverse 5–30 . Duncan and Truong reported a direct ab initio dynamics study of thermal and vibrationally state‐selected rates of this reaction 5 .…”

“…Based on a vibrationally diabatic model, they concluded that there is a significant enhancement in reaction rate when the CH 4 symmetric stretching mode is excited, which is subsequently confirmed by a recent experiment 31 . Several other potential energy surfaces (PESs) have been produced, 7–14 and used in quasiclassical trajectory studies (QCT) 11,14–17 and reduced dimensionality quantum dynamics calculations 8,9,18–21 . In addition, there have been direct dynamics calculations on this system 22,23 and numerous calculations based on variational transition state theory 6,7,10,14,24,25,27,29,30 …”

MEP–MPE potential energy surface for the Cl + CH4 → HCl + CH3 reaction

“…The dynamical full‐dimensional quasi‐classical calculations performed on the MEP–MPE PES indicate that the cone of acceptance is too large. As a matter of fact, the room temperature rate coefficient was estimated to be 29 2.07 ± 0.18 × 10 −13 cm 3 molecule −1 s −1 , a value twice as large as the IUPAC recommended one that is 1.0 cm 3 molecule −1 s −1 30.…”