✦ LIBER ✦

Kinetic study for the unimolecular dissociation of CF3H: RRKM and PST calculations on an ab initio potential energy surface

✍ Scribed by Dong Nam Shin; Yong Sim Yoo; Chul Woong Park; Jae Won Hahn; Kihyung Song

Publisher: Elsevier Science
Year: 1996
Tongue: English
Weight: 490 KB
Volume: 258
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(96)00691-4

No coin nor oath required. For personal study only.

✦ Synopsis

Unimolecular dissociations of CFaH into (1) CF2(1AI ) + HF, (2) CF 3 + H and (3) CF2H + F were studied by means of RRKM and PST calculations on an ab initio potential energy surface. Activation energies for the three channels (1), ( 2) and (3) are 73.95, 108.20 and 130.02 kcal/mol at G2 level, respectively. RRKM and PST calculations show that the reaction rate for channel (1) is significantly faster than that for channel (2) at low energy. As the internal energy increases, channel (2) becomes important and, at energies greater than 7.0 eV, competes with channel (1). These results are consistent with recent experimental observations.

📜 SIMILAR VOLUMES

AB INITIO CALCULATIONS OF THE POTENTIAL

AB INITIO CALCULATIONS OF THE POTENTIAL ENERGY SURFACES FOR THE UNIMOLECULAR DISSOCIATION REACTION OF ETHYLENE OXIDE

✍ Joseph J. Belbruno 📂 Article 📅 1997 🏛 John Wiley and Sons 🌐 English ⚖ 170 KB 👁 2 views

Ab initio calculations, including electron correlation, were employed to compute the geometries and energies of all stable C 2 H 4 O species, as well as four transition states along the potential surfaces connecting oxirane to the unimolecular dissociation products. The calculations indicate that th

Kinetic isotope effects for the H2 + C2H

Kinetic isotope effects for the H2 + C2H ↔ C2H2 + H reaction based on the ab initio calculations and a global potential energy surface

✍ Liping Ju; Dongsheng Wang 📂 Article 📅 2010 🏛 John Wiley and Sons 🌐 English ⚖ 184 KB

## Abstract In the present paper, kinetic isotope effects of the title reaction are studied with canonical variational transition state theory on the modified Wang Bowman (MWB) potential energy surface (PES) (__Chem Phys Lett__ 2005, 409, 249) and the ab initio calculations at the quadratic configu

Canonical statistical adiabatic channel

Canonical statistical adiabatic channel model calculations of the H + CH3 → CH4 recombination reaction on an ab initio potential energy surface. The role of the transitional modes

✍ C. J. Cobos 📂 Article 📅 1989 🏛 John Wiley and Sons 🌐 English ⚖ 517 KB

The canonical formalism of the statistical adiabatic channel model is used to calculate limiting high pressure rate constants for the H + CH, + CH4 recombination reaction on a recently reported analytic potential energy surface based on ab initio calculations. An effective adiabatic channel potentia

An ab initio Quantum Chemical and Kineti

An ab initio Quantum Chemical and Kinetic Study of the NNH + O Reaction Potential Energy Surface: How Important Is this Route to NO in Combustion?

✍ Naomi L. Haworth; John C. Mackie; George B. Bacskay 📂 Article 📅 2003 🏛 John Wiley and Sons ⚖ 58 KB 👁 2 views

Vinyloxyborane and its isomers. An ab in

Vinyloxyborane and its isomers. An ab initio study of the C2H5BO potential energy surface, the barrier to 1,3-shifts in β-ketoboranes, and the mechanism of the carbonylation reaction of boranes

✍ Mustafa R. Ibrahim; Michael Bühl; Reinhard Knab; Paul Von Rague Schleyer 📂 Article 📅 1992 🏛 John Wiley and Sons 🌐 English ⚖ 433 KB

Vinyloxyboranes, CH2=CH-O-BR2, are shown by ab initio molecular orbital theory to be more stable than the isomeric p-aldoboranes, R2B-CH2-CH=O, by ca. 19 kcal/mol. The MP2/6-31G\*/6-31G\* + ZPE barrier for the [1,3] boron shift is only 10.9 kcal/mol (R = Me) relative to the aldoborane. Other C,H,BO