Anharmonic effect of the dissociation rate constant of the unimolecular reactions of CH2XCHFO (X = H, F)

被引：6

作者：

Gu, Lingzheng ^{[1
]}

Yao, L. ^{[1
]}

Shao, Ying ^{[1
]}

Liu, Wei ^{[1
]}

Gao, Hong ^{[1
]}

机构：

[1] Dalian Maritime Univ, Dept Phys, Inst Computat Phys, Dalian 116026, Peoples R China

来源：

MOLECULAR PHYSICS | 2011年 / 109卷 / 16期

基金：

中国国家自然科学基金;

关键词：

anharmonic effect; unimolecular reaction; rate constant; RRKM theory; HYDROGEN ABSTRACTION REACTION; SPHERICAL-VESSEL METHOD; AB-INITIO; CH2FCH2F HFC-152; ATMOSPHERIC CHEMISTRY; CH3CHF2; HFC-152A; DIRECT DYNAMICS; RADICALS; STATES; FLUOROETHANES;

D O I：

10.1080/00268976.2011.602648

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

This study examines six unimolecular reactions of CH2XCHFO (X H, F). The geometries of the reactions are optimized with Gaussian 03. The calculated barrier heights show that bond C-C' scission, CH2XCHFO (X = H, F) -> CH2X+CHFO (R1), dominates the decomposition of CH2XCHFO. For X = F and X = F, the barrier heights of (R1) are 13.37 and 9.67 kcal mol(-1), respectively. The YL (Yao and Lin) method is used to calculate the anharmonic and harmonic rate constants of the unimolecular reactions. The results clearly demonstrate the anharmonic effect of these reactions. In the microcanonical case, for (R1) (X = H), the total energy is from 42.78 to 144.84 kcal mol(-1). The corresponding anharmonic rate constants are from 1.57 x 10(12) to 2.52 x 10(13) s(-1) and the harmonic rate constants are from 1.52 x 10(12) to 2.52 x 10(13) s(-1).

引用

页码：1983 / 1994

页数：12

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