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| 題名: | Reaction mechanisms and kinetics of the iminovinylidene radical with NO: Ab initio study |
| 作者: | Hsiao, Ming-Kai
Chung, Hua
Hung, Yu-Ming
Chen, Hui-Lung |
| 貢獻者: | 化學系 |
| 關鍵詞: | DENSITY-FUNCTIONAL THERMOCHEMISTRY
PRODUCT BRANCHING RATIOS
POTENTIAL-ENERGY SURFACE
TRANSITION-STATES
RATE CONSTANTS
ISOCYANOCARBENE HCNC
EQUILIBRIUM GEOMETRY
CYANOMETHYLENE HCCN
REACTION COORDINATE
CYANOCARBENE HCCN |
| 日期: | 2014-05-28 |
| 上傳時間: | 2015-01-26 10:55:53 (UTC+8) |
| 摘要: | The nitric oxide (NO) is a notorious compound for polluting environment. Recent year, removing nitric oxide from the atmosphere becomes a focus of the investigation. In our work, we study the iminovinylidene (HNCC) radical reacted with NO molecule. The mechanism and kinetic for reaction of the HNCC radical with the NO molecule is investigated via considering the possible channels of the N and O atoms of NO attacking the N and C atoms of the HNCC based on the high level ab initio molecular orbital calculations in conjunction with variational TST and RRKM calculations. The species involved have been optimized at the B3LYP/6-311++G(3df,2p) level and their single-point energies are refined by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) method. The calculated potential energy surfaces indicated that energetically the most favorable channel for the HNCC + NO reaction was predicted to be the formation of HNC+CNO (P8) product via the addition reaction of the C atom of HNCC radical and the N atom of NO with the head to head orientation. To rationalize the scenario of the calculated results, we also employ the Fukui functions and HSAB theory to seek for a possible explanation. In addition, the reaction rate constants were calculated using VariFlex code, and the results show that the total rate coefficient, k(total), at Ar pressure 760 Torr can be represented with an equation: k(total) = 6.433 x 10(-11) T (0.100) exp(0.275 kcal mol(-1)/RT) at T = 298-3000 K, in units of cm(3) molecule(-1) s(-1). (C) 2014 AIP Publishing LLC. |
| 關聯: | JOURNAL OF CHEMICAL PHYSICS 卷: 140 期: 20 文獻號碼: 204316 |
| 顯示於類別: | [化學系所] 期刊論文
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