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nco自由基
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  nco radical
     The results show that the reaction of CH3 radical with HNCO has three pathways :(1)CH3 radical reacts with HNCO to form a hydrogen-bond complex M of which the relative stable energy is 4.56 kJ·mol-1,and then forms another complex M′ t hrough a transition state TS, and breaks down into CH4 and NCO radical in the en d.
     结果表明,自由基CH3与HNCO分子间反应有三条反应通道,第一为CH3与HNCO分子间经过生成一个稳定化能为4.56kJ·mol-1的含氢键的分子复合物M后,经过渡态TS生成另一个产物复合物M',然后分解为甲烷和NCO自由基;
短句来源
  相似匹配句对
     FREE RADICAL'S SCAVENGING
     自由基的清除
短句来源
     Quenching of NCO( A~ 2Σ~+) Radicals by Alkane Molecules
     烷烃类分子对NCO(A~2Σ~+)自由基的猝灭
短句来源
     KINESTIC ABILITY AND FREE RADICAL
     运动能力与自由基
短句来源
     Design of NCO Based on DDS
     基于DDS的NCO设计
短句来源
     A new study method of analyzing reaction mechanism is presented.
     第四章用密度泛函理论研究了F原子与自由基NCO在3A″势能面上的反应。
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  nco radical
The spectrometer has been applied to high resolution spectroscopy of the NCO radical at 5.2 μm.
      
41 lines of the antisymmetric stretching-vibrationv3 of the linear NCO radical have been observed.
      


NCO radicals were produced by laser photolysis of CHBr 3 at 266 nm followed by the reaction of CH with N 2O. The electronic ground state NCO radicals were electronically excited to A 2Σ +(00 00) state by laser irradiation at 438.6 nm. The quenching rate constants of NCO ( A 2Σ +) by CH 4, n C 5H 12 , c C 6H 12 , n C 6H 14 , n C 7H 16 , n C 8H 18 were measured by investigating the time resolved fluorescence from the excited NCO in room temperature...

NCO radicals were produced by laser photolysis of CHBr 3 at 266 nm followed by the reaction of CH with N 2O. The electronic ground state NCO radicals were electronically excited to A 2Σ +(00 00) state by laser irradiation at 438.6 nm. The quenching rate constants of NCO ( A 2Σ +) by CH 4, n C 5H 12 , c C 6H 12 , n C 6H 14 , n C 7H 16 , n C 8H 18 were measured by investigating the time resolved fluorescence from the excited NCO in room temperature (298 K). Removal was found to be very efficient where the rate constants with the above gases were measured as 2.35±0.14, 4.74±0.11, 4.65±0.12, 4.84±0.21, 5.15±0.19, 5.51±0.26, respectively, in units of 10~10 cm 3/molec s. It is shown that the quenching rate constants and cross sections of NCO ( A 2Σ +) increase almost linearly with increasing the number of C-H bonds contained in the alkane molecules. By analysis, it is thought that chemical reactions play an important role in the quenching of the electronically excited NCO radicals and in addition to chemical reaction, collisional removal of NCO ( A 2Σ +) can take place via an E-V energy transfer.

采用激光光解 激光诱导荧光 (LP LIF)的方法 ,用 2 6 6nm激光光解CHBr3 分子产生CH自由基 ,再与N2 O继续反应作为NCO自由基的产生源 ,用 4 38.6nm激光将电子基态X 2 Πi(0 0 10 )的NCO激励到激发态A2 Σ+ (0 0 0 0 )上 ,通过检测激发态NCO时间分辨荧光信号 ,测得室温 (2 98K)下NCO(A2Σ+ )被烷烃类分子猝灭的实验结果 ,获得了A 2Σ+ (0 0 0 0 )态猝灭速率常数 .实验发现 ,随着烷烃分子中C -H键数增加 ,其猝灭截面也近线性增加 ,但随着分子体积增大 ,这种增加趋缓 .

Ab initio UMP2 method was used to study the reaction mechanism of CH3 radical with HNCO. The geometric configurations of reactants, products, interme diates and transition states were optimized at UMP2(full)/6-311++G level . The results show that the reaction of CH3 radical with HNCO has three pathways :(1)CH3 radical reacts with HNCO to form a hydrogen-bond complex M of which the relative stable energy is 4.56 kJ·mol-1,and then forms another complex M′ t hrough a transition state TS, and breaks down into...

Ab initio UMP2 method was used to study the reaction mechanism of CH3 radical with HNCO. The geometric configurations of reactants, products, interme diates and transition states were optimized at UMP2(full)/6-311++G level . The results show that the reaction of CH3 radical with HNCO has three pathways :(1)CH3 radical reacts with HNCO to form a hydrogen-bond complex M of which the relative stable energy is 4.56 kJ·mol-1,and then forms another complex M′ t hrough a transition state TS, and breaks down into CH4 and NCO radical in the en d. (2)CH3 radical reacts with HNCO to form a stable trans-intermediate(trans-int), then through a transition state(trans-ts) breaks down into CH3NH and CO . (3)CH3 radical reacts with HNCO to form a stable cis-intermediate(cis-int), and then through a transition state(cis-ts) breaks down into CH3NH and CO. Com paring the activation energy of the three pathways, we can draw a conclusion th at the pathway of forming CH4 and NCO radical is more feasible.

在6-311++G基组水平上,采用UMP2方法对自由基CH3与HNCO反应机理进行了研究,全参数优化了反应通道上各驻点的几何构型.结果表明,自由基CH3与HNCO分子间反应有三条反应通道,第一为CH3与HNCO分子间经过生成一个稳定化能为4.56kJ·mol-1的含氢键的分子复合物M后,经过渡态TS生成另一个产物复合物M',然后分解为甲烷和NCO自由基;第二是CH3与HNCO分子间通过生成稳定反式中间体trans-int,其经过渡态trans-ts分解成产物CH3NH和CO;第三是CH3与HNCO分子间通过生成稳定顺式中间体cis-int,其经过渡态cis-ts分解成产物CH3NH和CO.比较三条反应通道的反应活化能,表明CH3与HNCO反应较易生成CH4+NCO.

The reactions of NCO with SO2 or CS2 in gas phase under total pressure of 2660 Pa and 298 K were studied by laser photolysis/laser induced fluorescence (LP/LIF).The NCO radicals were produced by laser photolysis of CHBr3 at 266 nm followed by the reaction of the produced CH in the photolysis reaction with NO.The relative concentration of ground states NCO radicals were monitored by time resolved LIF spectra.From the results of time resolved measurements on the NCO radicals,the bimolecular rate constants for...

The reactions of NCO with SO2 or CS2 in gas phase under total pressure of 2660 Pa and 298 K were studied by laser photolysis/laser induced fluorescence (LP/LIF).The NCO radicals were produced by laser photolysis of CHBr3 at 266 nm followed by the reaction of the produced CH in the photolysis reaction with NO.The relative concentration of ground states NCO radicals were monitored by time resolved LIF spectra.From the results of time resolved measurements on the NCO radicals,the bimolecular rate constants for the reactions of NCO with SO2 and CS2 were obtained as (1.8± 0.3)× 10- 11 and (3.1± 0.4)× 10- 12 cm3· molecule- 1· s- 1, respectively.In addition,the two reactions were studied using ab initio calculations at the B3LYP/6 31+ G(d) level.The results show that both are addition reactions and have the similar mechanism in which N atom of NCO radical attacks the central atom of SO2 or CS2 to form addition product.

利用波长为266nm的激光光解CHBr3产生CH自由基,其与NO反应作为NCO自由基的来源.在298K,总压2660Pa的条件下,采用激光诱导荧光的方法,研究了NCO自由基与SO2、CS2的反应.得到了NCO自由基与SO2、CS2双分子反应速率常数分别为(1.8±0.3)×10-11和(3.1±0.4)×10-12cm3·molecule-1·s-1.对这两个反应在B3LYP/6-31+G(d)的水平上进行理论研究的结果表明,NCO自由基与SO2、CS2的反应是加成反应,其机理是NCO自由基中的N原子攻击反应物的中心原子,得到加成产物.

 
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