Quantum Chemical Prediction of Pathways and Rate Constants for Reaction of Cyanomethylene Radical with NO

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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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