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https://irlib.pccu.edu.tw/handle/987654321/24077
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| 题名: | Quantum Chemical Prediction of Pathways and Rate Constants for Reaction of Cyanomethylene Radical with NO |
| 作者: | Chen, HL (Chen, Hui-Lung)
Chao, WC (Chao, Wan-Chun) |
| 贡献者: | Dept Chem |
| 关键词: | DENSITY-FUNCTIONAL THERMOCHEMISTRY
PRODUCT BRANCHING RATIOS
POTENTIAL-ENERGY SURFACE
TRANSITION-STATES;AB-INITIO
ISOCYANOCARBENE HCNC
REACTION-MECHANISMS
EQUILIBRIUM GEOMETRY
REACTION COORDINATE
CYANOCARBENE HCCN |
| 日期: | 2011-02-17 |
| 上传时间: | 2013-01-25 10:05:03 (UTC+8) |
| 摘要: | High-level ab initio calculations have been per formed to study the mechanism and kinetics of the reaction of the cyanomethylene radical (HCCN) with the NO The species involved have been optimized at the B3LYP/6-311++G-(3df,2p) level, and their corresponding single point energies are improved by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) approach. From the calculated potential energy surface, we have predicted the favorable pathways for the formation of several isomers of a HCCN-NO complex. Barrierless formation of HCN + NCO (P1) is also possible. Formation of HCNO + CN (P3) is endoergic but may become significant at high temperatures. To rationalize the scenario of our calculated results, we also employ the Fukui functions and hard-and-soft acid-and-base (HSAB) theory to seek possible clues. The predicted total rate coefficient, k(total), at He pressure 760 Torr can be represented with the equation k(total) = 1.40 x 10(-7) T(-2.01) exp(3.15 kcal mol(-1)/RT) at T = 298-3000 K in units of cm(3) molecule(-1) s(-1). The predicted total rate coefficients at some available conditions (He pressures of 6, 18, and 30 Torr in the temperature of 298 K) are in reasonable agreement with experimental observation. In addition, the rate constants for key individual product channels are provided in different temperature and pressure conditions |
| 關聯: | JOURNAL OF PHYSICAL CHEMISTRY A 卷: 115 期: 6 頁數: 1133-1142 |
| 显示于类别: | [化學系所] 期刊論文
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