系列氰化物与活泼自由基反应的理论研究
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摘要
氰化物（如HCN，CH_3CN,C_2H_5CN,CF_3CN,CH_2CHCN等）是一类重要的挥发性有机物，其释放到大气中，会对人类和环境造成危害，因此研究它们在大气中的转化和吸收显得尤为重要，其中主要的吸收途径是它们与活泼自由基(如OH，Cl，F，O等)的反应，但是这些反应非常复杂而且反应速度很快，反应过程中会产生很多自由基和分子，为实验研究带来了困难。因此本文从理论角度出发，应用现有的量子化学理论和方法，详细地研究了一系列氰化物与活泼自由基的反应机理，并计算了反应速率常数，对反应过程进行理论预测。
多通道气相反应的微观机理和速率常数的计算一直是化学反应动力学研究的难点，因此我们在这方面进行了探索和尝试，获得的主要成果如下：
1.应用量子化学方法研究了H与C_2H_5CN的反应机理和动力学性质。通过B3LYP/6-311+G(d,p)和B3LYP/6-311+G(2d,2p)方法得到反应涉及的中间体及过渡态的几何结构，在B3LYP/6-311+G(2d,2p)的几何构型基础上，应用G3和BMC-CCSD方法得到各物种的高水平能量，并在G3//B3LYP6-311+G(2d,2p)水平上得到反应精确的势能面。反应涉及四种反应机理，即氢提取，C-加成/消除，N-加成/消除和取代。对于反应的动力学行为，应用过渡态和多通道RRKM理论进行研究，得到了反应在温度为200-3000K的速率常数。计算表明在整个温度区间，C-加成/消除通道为主要的反应路径。在低温区间，最初加成物C2H5CHN的去活化过程是主要的；在高温区间，产物C_2H_5+HCN是主要的。
2.应用G3(MP2)//B3LYP/6-311+G(d,p)方法给出了氧原子与CH_3CN反应的单重态和三重态势能面。在三重态势能面上，发现六种反应机理，即直接氢提取，C-加成/消除，N-加成/消除，取代，插入和氢迁移。应用过渡态理论和多通道RRKM理论来研究总速率常数和分支速率常数随温度及压力的变化情况。结果表明在三重态势能面上直接氢提取和C-加成/消除是主要的反应路径，主要的产物是CH_3+NCO和CH_2CN+OH。在大气压力下，Ar和N_2作为碰撞气体，温度低于700K时，IM1(CH_3C(O)N)的碰撞失活是主要的；而在800-1500K，由C-加成/消除机理生成的CH_3+NCO产物是主要的；在高温（如燃烧温度）由直接氢提取机理生成的CH_2CN+OH是主要的产物。更重要的是，计算的速率常数与实验测定的速率常数相符合。同时也计算了三重态反应的同位素效应，结果表明同位素效应并不显著。在单重态势能面上，反应机理与三重态反应有很大不同，氧原子会很容易插入到CH_3CN的C-H或者C-C键生成中间体s-IM8(HOCH_2CN)和s-IM5(CH_3OCN)或者加成到CH3CN中-CN基团的碳原子上生成中间体s-IM1(CH_3C(O)N)，这些过程均是无垒过程。
3.在氧原子与CH_3CN反应的基础上，我们应用量子化学方法研究了O(3~P和1~D)与CF_3CN的反应机理和动力学行为。在QCISD(T)/6-311+G(2df)//B3LYP/6-311+G(d)水平上获得单重态和三重态势能面。在三重态势能面上，存在六种反应机理，即直接氟提取，C-加成/消除，N-加成/消除，取代，插入和氟迁移。结果表明主要的反应机理是C-加成/消除，中间体的去活化产物CF_3C(O)N以及中间体的分解产物CF_3+NCO占主要。应用RRKM理论对C-加成/消除通道的速率常数进行了计算，并与实验值进行了比较。而对于单重态势能面，插入机理为主要的反应机理，氧原子能够经过无垒过程插入到CF_3CN的C-F及C-C键中，生成FOCF_2CN和CF_3OCN；也能加成到CF_3CN的-CN基团的碳原子和氮原子上，生成中间体CF_3C(O)N和CF_3CNO。同时对中间体的分解和异构化过程进行了详细研究。
4.丙烯腈的主要吸收途径是与羟基的反应。基于此，我们应用量子化学方法研究了该反应的详细机理和动力学性质。CH_2=CHCN是不饱和化合物，CH_2=CHCN与OH的反应如同OH与CH_2=CH_2及CH_2=CHCH_3的反应，会生成前期复合物。本文中采用BHandHLYP和M05-2X方法进行几何构型优化，BMC-CCSD方法获得能量信息。反应机理表明OH能够通过低能垒过程加成到C=C双键及-CN基团的碳原子上，生成中间体1-IM1(HOCH_2CHCN),2-IM1(CH_2HOCHCN),和3-IM1(CH_2CHCOHN)，同时会发生直接氢提取反应机理。应用RRKM理论来研究速率常数随温度和压力的变化情况，计算值与实验值相符合。在一个大气压下，N_2作为碰撞气体，温度为200-1200K时，1-IM1(OHCH_2CHCN)是主要的产物，而在高温区间（1200-3000K），由直接氢提取生成的产物CH_2CCN和CHCHCN及H_2O是主要的。
Cyanides (such as hydrogen cyanide, methyl cyanide, ethyl cyanide,Cyanotrifluoromethane, acrylonitrile and so on) are one of the most important classes ofvolatile organic compounds (VOCs). They are harmful for human and environment when theyrelease into atmosphere. Thus it is especially important for cyanides to be translated andabsorbed. The dominant absorption way is the reactions with radicals (e.g., OH, Cl, F, O).Experimentally these reactions are hard to research because they are very complex and fast,and could also produce many free radicals and molecules. Therefore, in our paper, quantumchemistry theories and methods are employed to research reaction mechanism and kinetics ofcyanides with active free radicals, and these results would provide some theoretical prospect.
During the investigation of reaction dynamics, the difficulty is reaction mechanism andkinetics of multi-channel gas phase reactions. In our paper, the efforts are made to explore andinvestigate these aspects. The results in the thesis are summaried as follows:
1. The reaction of H radical with C_2H_5CN had been studied using various quantumchemistry methods. The geometries were optimized at the B3LYP/6-311+G(d,p) andB3LYP/6-311++G(2d,2p) levels. The single-point energies were calculated using G3andBMC-CCSD methods based on B3LYP/6-311++G(2d,2p) geometries. The potential energysurface was obtained at the G3//B3LYP6-311+G(2d,2p) level. Four mechanisms wereinvestigated, namely, hydrogen abstraction, C-addition/elimination, N-addition/eliminationand substitution. The kinetics of this reaction were studied using the transition state theory(TST) and multichannel RRKM methodologies over a wide temperature range of200-3000K.The calculated results indicated that C-addition/elimination channel was the most feasibleover the whole temperature range. The deactivation of initial adduct C_2H_5CHN was dominantat lower temperature; while C_2H_5+HCN was the dominant product at higher temperature.
2. The low-lying triplet and singlet potential energy surfaces of the O(~3P)+CH_3CNreaction had been studied at the G3(MP2)//B3LYP/6-311+G(d,p) level. On the triplet surface,six kinds of pathways were revealed, namely, direct hydrogen abstraction,C-addition/elimination, N-addition/elimination, substitution, insertion and H-migration.Multichannel RRKM theory and transition state theory were employed to calculate the overalland individual rate constants over a wide range of temperatures and pressures. It waspredicted that the direct hydrogen abstraction and C-addition/elimination on triplet potentialenergy surface were dominant pathways. Major predicted end-products included CH_3+NCOand CH_2CN+OH. At atmospheric pressure with Ar and N_2as bath gases, CH3C(O)N (IM1)formed by collisional stabilization was dominated at T<700K, whereas CH3+NCO producedby C-addition/elimination pathway were the major products at the temperatures between800and1500K; the direct hydrogen abstraction leading to CH_2CN+OH played an important roleat higher temperatures in hydrocarbon combustion chemistry and flames, with estimatedcontribution of64%at2000K. Furthermore, the calculated rate constants were in good agreement with available experimental data over the temperature range300-600K. Thekinetic isotope effect (KIE) had also been calculated for the triplet O(~3P)+CH_3CN reaction,and it isn’t important. It was indicated that the singlet reaction exhibited a marked differencefrom the triplet reaction. On the singlet surface, the atomic oxygen could easily insert intoC─H or C─C bonds of CH_3CN, forming the insertion intermediates s-IM8(HOCH_2CN) ands-IM5(CH_3OCN) or added to the carbon atom of-CN group in CH3CN, forming the additionintermediate s-IM1(CH3C(O)N); both approaches were found to be barrierless.3. Along with the investigation of O(~3P) with CH3CN reaction, the quantum chemicalmethods had been employed to investigate the mechanism and kinetics of O(3P and1D) withCF3CN reaction. The singlet and triplet potential energy surfaces had been obtained at theQCISD(T)/6-311+G(2df)//B3LYP/6-311+G(d) level. On the triplet surface, six kinds ofpathways were revealed, namely, direct fluorine abstraction, C-addition/elimination,N-addition/elimination, substitution, insertion and F-migration. The results showed that thereaction should occur mainly through C-addition/elimination mechanism involving thechemically activated CF_3C(O)N*intermediate and the major products are CF_3and NCO. Therate constants for C-addition/elimination channel of O(~3P) with CF_3CN reaction had beendetermined by using RRKM statistical rate theory and compared with the experimental data.On the singlet surface, the insertion mechanism was important. The atomic oxygen couldeasily insert into C─F or C─C bond of CF_3CN, forming the insertion intermediates FOCF2CNand CF_3OCN. And O(1D) could add to the carbon or nitrogen atom of-CN group in CF_3CN,forming the addition intermediates CF_3C(O)N and CF_3CNO; both approaches were found tobe barrierless. The decomposition and isomerization of some intermediates were alsoperformed.4. The reaction of OH with CH_2CHCN was revealed to be one of the most significantloss processes of acrylonitrile. Therefore, mechanism and kinetics of the reaction ofacrylonitrile (CH2CHCN) with hydroxyl (OH) had been investigated. CH2CHCN belongsto unsaturated compound, and the reaction of OH with CH_2CHCN is as the same as the OHwith CH_2=CH_2and CH_2=CHCH_3reactions, the pre-reactive complex would be formed.BHandHLYP and M05-2X methods were employed to obtain initial geometries. The reactionmechanism conformed that OH addition to C=C double bond or C atom of-CN group formedthe chemically activated adducts,1-IM1(HOCH_2CHCN),2-IM1(CH_2HOCHCN), and3-IM1(CH_2CHCOHN) via low barriers, and direct hydrogen abstraction paths may alsooccur. Temperature-and pressure-dependent rate constants had been evaluated using RRKMtheory. The calculated rate constants were in good agreement with the experimental data. Atatmospheric pressure with N_2as bath gas,1-IM1(OHCH_2CHCN) formed by collisionalstabilization was the major product in the temperature range of200-1200K. The productionof CH_2CCN and CHCHCN via hydrogen abstraction became dominant at high temperatures(1200-3000K).
多通道气相反应的微观机理和速率常数的计算一直是化学反应动力学研究的难点，因此我们在这方面进行了探索和尝试，获得的主要成果如下：
1.应用量子化学方法研究了H与C_2H_5CN的反应机理和动力学性质。通过B3LYP/6-311+G(d,p)和B3LYP/6-311+G(2d,2p)方法得到反应涉及的中间体及过渡态的几何结构，在B3LYP/6-311+G(2d,2p)的几何构型基础上，应用G3和BMC-CCSD方法得到各物种的高水平能量，并在G3//B3LYP6-311+G(2d,2p)水平上得到反应精确的势能面。反应涉及四种反应机理，即氢提取，C-加成/消除，N-加成/消除和取代。对于反应的动力学行为，应用过渡态和多通道RRKM理论进行研究，得到了反应在温度为200-3000K的速率常数。计算表明在整个温度区间，C-加成/消除通道为主要的反应路径。在低温区间，最初加成物C2H5CHN的去活化过程是主要的；在高温区间，产物C_2H_5+HCN是主要的。
2.应用G3(MP2)//B3LYP/6-311+G(d,p)方法给出了氧原子与CH_3CN反应的单重态和三重态势能面。在三重态势能面上，发现六种反应机理，即直接氢提取，C-加成/消除，N-加成/消除，取代，插入和氢迁移。应用过渡态理论和多通道RRKM理论来研究总速率常数和分支速率常数随温度及压力的变化情况。结果表明在三重态势能面上直接氢提取和C-加成/消除是主要的反应路径，主要的产物是CH_3+NCO和CH_2CN+OH。在大气压力下，Ar和N_2作为碰撞气体，温度低于700K时，IM1(CH_3C(O)N)的碰撞失活是主要的；而在800-1500K，由C-加成/消除机理生成的CH_3+NCO产物是主要的；在高温（如燃烧温度）由直接氢提取机理生成的CH_2CN+OH是主要的产物。更重要的是，计算的速率常数与实验测定的速率常数相符合。同时也计算了三重态反应的同位素效应，结果表明同位素效应并不显著。在单重态势能面上，反应机理与三重态反应有很大不同，氧原子会很容易插入到CH_3CN的C-H或者C-C键生成中间体s-IM8(HOCH_2CN)和s-IM5(CH_3OCN)或者加成到CH3CN中-CN基团的碳原子上生成中间体s-IM1(CH_3C(O)N)，这些过程均是无垒过程。
3.在氧原子与CH_3CN反应的基础上，我们应用量子化学方法研究了O(3~P和1~D)与CF_3CN的反应机理和动力学行为。在QCISD(T)/6-311+G(2df)//B3LYP/6-311+G(d)水平上获得单重态和三重态势能面。在三重态势能面上，存在六种反应机理，即直接氟提取，C-加成/消除，N-加成/消除，取代，插入和氟迁移。结果表明主要的反应机理是C-加成/消除，中间体的去活化产物CF_3C(O)N以及中间体的分解产物CF_3+NCO占主要。应用RRKM理论对C-加成/消除通道的速率常数进行了计算，并与实验值进行了比较。而对于单重态势能面，插入机理为主要的反应机理，氧原子能够经过无垒过程插入到CF_3CN的C-F及C-C键中，生成FOCF_2CN和CF_3OCN；也能加成到CF_3CN的-CN基团的碳原子和氮原子上，生成中间体CF_3C(O)N和CF_3CNO。同时对中间体的分解和异构化过程进行了详细研究。
4.丙烯腈的主要吸收途径是与羟基的反应。基于此，我们应用量子化学方法研究了该反应的详细机理和动力学性质。CH_2=CHCN是不饱和化合物，CH_2=CHCN与OH的反应如同OH与CH_2=CH_2及CH_2=CHCH_3的反应，会生成前期复合物。本文中采用BHandHLYP和M05-2X方法进行几何构型优化，BMC-CCSD方法获得能量信息。反应机理表明OH能够通过低能垒过程加成到C=C双键及-CN基团的碳原子上，生成中间体1-IM1(HOCH_2CHCN),2-IM1(CH_2HOCHCN),和3-IM1(CH_2CHCOHN)，同时会发生直接氢提取反应机理。应用RRKM理论来研究速率常数随温度和压力的变化情况，计算值与实验值相符合。在一个大气压下，N_2作为碰撞气体，温度为200-1200K时，1-IM1(OHCH_2CHCN)是主要的产物，而在高温区间（1200-3000K），由直接氢提取生成的产物CH_2CCN和CHCHCN及H_2O是主要的。
Cyanides (such as hydrogen cyanide, methyl cyanide, ethyl cyanide,Cyanotrifluoromethane, acrylonitrile and so on) are one of the most important classes ofvolatile organic compounds (VOCs). They are harmful for human and environment when theyrelease into atmosphere. Thus it is especially important for cyanides to be translated andabsorbed. The dominant absorption way is the reactions with radicals (e.g., OH, Cl, F, O).Experimentally these reactions are hard to research because they are very complex and fast,and could also produce many free radicals and molecules. Therefore, in our paper, quantumchemistry theories and methods are employed to research reaction mechanism and kinetics ofcyanides with active free radicals, and these results would provide some theoretical prospect.
During the investigation of reaction dynamics, the difficulty is reaction mechanism andkinetics of multi-channel gas phase reactions. In our paper, the efforts are made to explore andinvestigate these aspects. The results in the thesis are summaried as follows:
1. The reaction of H radical with C_2H_5CN had been studied using various quantumchemistry methods. The geometries were optimized at the B3LYP/6-311+G(d,p) andB3LYP/6-311++G(2d,2p) levels. The single-point energies were calculated using G3andBMC-CCSD methods based on B3LYP/6-311++G(2d,2p) geometries. The potential energysurface was obtained at the G3//B3LYP6-311+G(2d,2p) level. Four mechanisms wereinvestigated, namely, hydrogen abstraction, C-addition/elimination, N-addition/eliminationand substitution. The kinetics of this reaction were studied using the transition state theory(TST) and multichannel RRKM methodologies over a wide temperature range of200-3000K.The calculated results indicated that C-addition/elimination channel was the most feasibleover the whole temperature range. The deactivation of initial adduct C_2H_5CHN was dominantat lower temperature; while C_2H_5+HCN was the dominant product at higher temperature.
2. The low-lying triplet and singlet potential energy surfaces of the O(~3P)+CH_3CNreaction had been studied at the G3(MP2)//B3LYP/6-311+G(d,p) level. On the triplet surface,six kinds of pathways were revealed, namely, direct hydrogen abstraction,C-addition/elimination, N-addition/elimination, substitution, insertion and H-migration.Multichannel RRKM theory and transition state theory were employed to calculate the overalland individual rate constants over a wide range of temperatures and pressures. It waspredicted that the direct hydrogen abstraction and C-addition/elimination on triplet potentialenergy surface were dominant pathways. Major predicted end-products included CH_3+NCOand CH_2CN+OH. At atmospheric pressure with Ar and N_2as bath gases, CH3C(O)N (IM1)formed by collisional stabilization was dominated at T<700K, whereas CH3+NCO producedby C-addition/elimination pathway were the major products at the temperatures between800and1500K; the direct hydrogen abstraction leading to CH_2CN+OH played an important roleat higher temperatures in hydrocarbon combustion chemistry and flames, with estimatedcontribution of64%at2000K. Furthermore, the calculated rate constants were in good agreement with available experimental data over the temperature range300-600K. Thekinetic isotope effect (KIE) had also been calculated for the triplet O(~3P)+CH_3CN reaction,and it isn’t important. It was indicated that the singlet reaction exhibited a marked differencefrom the triplet reaction. On the singlet surface, the atomic oxygen could easily insert intoC─H or C─C bonds of CH_3CN, forming the insertion intermediates s-IM8(HOCH_2CN) ands-IM5(CH_3OCN) or added to the carbon atom of-CN group in CH3CN, forming the additionintermediate s-IM1(CH3C(O)N); both approaches were found to be barrierless.3. Along with the investigation of O(~3P) with CH3CN reaction, the quantum chemicalmethods had been employed to investigate the mechanism and kinetics of O(3P and1D) withCF3CN reaction. The singlet and triplet potential energy surfaces had been obtained at theQCISD(T)/6-311+G(2df)//B3LYP/6-311+G(d) level. On the triplet surface, six kinds ofpathways were revealed, namely, direct fluorine abstraction, C-addition/elimination,N-addition/elimination, substitution, insertion and F-migration. The results showed that thereaction should occur mainly through C-addition/elimination mechanism involving thechemically activated CF_3C(O)N*intermediate and the major products are CF_3and NCO. Therate constants for C-addition/elimination channel of O(~3P) with CF_3CN reaction had beendetermined by using RRKM statistical rate theory and compared with the experimental data.On the singlet surface, the insertion mechanism was important. The atomic oxygen couldeasily insert into C─F or C─C bond of CF_3CN, forming the insertion intermediates FOCF2CNand CF_3OCN. And O(1D) could add to the carbon or nitrogen atom of-CN group in CF_3CN,forming the addition intermediates CF_3C(O)N and CF_3CNO; both approaches were found tobe barrierless. The decomposition and isomerization of some intermediates were alsoperformed.4. The reaction of OH with CH_2CHCN was revealed to be one of the most significantloss processes of acrylonitrile. Therefore, mechanism and kinetics of the reaction ofacrylonitrile (CH2CHCN) with hydroxyl (OH) had been investigated. CH2CHCN belongsto unsaturated compound, and the reaction of OH with CH_2CHCN is as the same as the OHwith CH_2=CH_2and CH_2=CHCH_3reactions, the pre-reactive complex would be formed.BHandHLYP and M05-2X methods were employed to obtain initial geometries. The reactionmechanism conformed that OH addition to C=C double bond or C atom of-CN group formedthe chemically activated adducts,1-IM1(HOCH_2CHCN),2-IM1(CH_2HOCHCN), and3-IM1(CH_2CHCOHN) via low barriers, and direct hydrogen abstraction paths may alsooccur. Temperature-and pressure-dependent rate constants had been evaluated using RRKMtheory. The calculated rate constants were in good agreement with the experimental data. Atatmospheric pressure with N_2as bath gas,1-IM1(OHCH_2CHCN) formed by collisionalstabilization was the major product in the temperature range of200-1200K. The productionof CH_2CCN and CHCHCN via hydrogen abstraction became dominant at high temperatures(1200-3000K).
引文
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