苯胺激发态的动力学及醛类与小分子反应动力学的理论研究
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摘要
本文主要做了三方面的工作如下：第一部分是苯胺激发态动力学方面的研究；第二部分为甲醛与臭氧的反应机理和动力学的研究；第三部分是乙醛与甲氧基自由基的反应机理和动力学的研究。
在苯胺激发态动力学方面的研究中，我们首先需要构建模型哈密顿函数，耦合多方面的参数，这里包括了苯胺的六个电子态。采用K ppel等人的二次振动耦合哈密顿算符。这些参数是通过拟合大量的运动方程耦合簇原理，以及双激发的EOM-CCSD方法得到的。在4.0–6.0eV区域进行了吸收光谱的计算和分析。
基于二次振动耦合模型的哈密顿算符用于研究苯胺的电子吸收光谱。拟合了大量的EOM-CCSD计算结果得到模型哈密顿函数的参量。与CASSCF和SAC-CI相比，EOM-CCSD方法得到的结果在第二个ππ*态附近有2个3p里德伯态。采用CR-EOM-CCSD(T)方法得到的结果与EOM-CCSD一致。
采用模型哈密顿函数，波包传播计算了激发到A (ππ*)和B (π*/3s)态的吸收光谱，其中发现A (ππ*)和C (3pz)有强烈的耦合作用。对于A (ππ)光谱，线性偶极激发算符，以及Herzberg-Teller效应的运用显得至关重要。
激发到E (ππ)的光谱，通过模型哈密顿函数能非常好的表示出来。短时动力学研究表明，D (3py)和C (3pz)态表现活跃。但是实验提出的从E (ππ)态到基态的最有可能的路径没有包含在模拟中，因为在模型中没有设置S1/S0交叉点的存在。所以下一步的工作希望能找出更合理的模型势能函数，包含更合理的构型区间。
第二部分研究了甲醛与臭氧的反应机理和动力学性质。
甲醛和臭氧广泛存在于地球表面大气层中。近些年，臭氧机被用来―减少‖室内污染物。然而通过臭氧机与室内不饱和有机物的反应会产生醛类产物，这使得室内污染物并没有减少，反而加大了危害。尽管甲醛和臭氧的反应在很早就开始了研究，但是远没像乙醛与臭氧反应那样受到重视。Li等人开展了用臭氧去除室内甲醛的实验研究，结果发现其反应速率低，效果不佳。
采用BMC-CCSD//BHandHLYP/6-311+G(d,p)方法计算了甲醛(CH2O)和臭氧(O3)在单重态和三重态上的势能面。提出了多条可能的异构化和解离反应路径。在单重态和三重态势能面上均找到了氢提取，氧提取，碳加成消除这三类反应通道。反应的主要通道是通过氢提取过程生成HCO和HOOO。采用过渡态(TST)理论和多通道RRKM理论计算了多个温度和压力下主要通道的反应速率和总速率，反映出温度强依赖和压力弱依赖的性质。
第三部分是乙醛与甲氧基自由基的反应机理和动力学性质的研究。
甲氧基是有机物燃烧的重要中间体，特别是在挥发性有机化合物的氧化过程中，广泛存在。此外，乙醛虽然是一种大气污染物，但也能用来消除空气中部分挥发性有机化合物。不管是生物作用还是人类活动，都大量产生这两种物质。甲氧基作为最小的烷氧基与乙醛这种最典型的醛类反应的研究，有很重要的意义。
采用了密度泛函(B3LYP)理论和从头算电子相关(MP2)方法，结合6-311+G(d,p)基组进行了构型的优化。因MP2方法有较大的自旋污染，且与实验构型比较也没有B3LYP方法好，所以采用了B3LYP优化后的构型。在BMC-QCISD//(U)B3LYP/6-311+G(d,p)水平下进行了势能面的系统研究，发现醛基中的氢提取，生成CH3CO和CH3OH为主反应，与实验结果一致。并得出在298K时的速率常数为8.73E-15cm3molecule-1s-1，与实验结果符合得非常好(8.30E-15cm3molecule-1s-1)。对于形成P3和P4的加成消除反应通道，我们推测不是传统的醛类的亲核加成消除反应，但可以用轨道理论进行解释。中间体IM1通过乙醛的HOMO(π轨道)和甲氧基中的LUMO(π*轨道)加成得到。运用过渡态理论和多通道的RRKM理论，我们发现该体系对温度有强依赖，氢提取对压力没有依赖，加成消除反应对压力有一定的依赖，但是在总速率中所占比率太小，所以总反应对压力是没有依赖的。
Formaldehyde (CH2O) and ozone (O3) are ubiquitous species in the atmosphereand at the surface of the Earth. Formaldehyde is a significant pro-knock additive ofthe methane-base fue and is particularly an important intermediate in the oxidation ofalcohols, ethers, and hydrocarbons in general. Moreover, formaldehyde leads to largeaccumulation in air and final pollution because of the thermodynamic stability.Therefore, it causes an environmental concern, especially influence of indoorformaldehyde on health. In recent years, the use of ozone intentionally produced by anozone generator, has been promoted as a means to―reduce‖the concentration ofindoor pollutants. However, reactions between ozone and certain unsaturated organiccompounds in indoor environments have been shown to generate large amount ofaldehydes, which are more reactive and/or irritating than their precursors. Therefore,the consequences of the emission of formaldehyde have been the object of severalstudies. Though the emissions of formaldehyde are related to the ozone as statedearlier, less attention was paid to the reaction of aldehyde with ozone. The relevantkinetic data are desirable to understand the reaction mechanism, to establish theimpact on the ozone, and perform kinetics modeling for the chemical process ofindoor environments. Li et al. experimentally investigated the ozone on removingindoor formaldehyde, and they found that ozone was not effective in formaldehyderemoval through releasing ozone into the room because of the small rate constant.
Much attention has been paid recently to the photochemistry and photophysics ofsmall heteroaromatic molecules, such as phenols, indoles and pyrroles. Such interesthas been invoked partly due to their being analogues of the chromophores ofbiologically important molecules, including the DNA bases and aromatic amino acids.This class of molecules is remarkable for their low fluorescence quantum yields, aproperty that has it’s origins in efficient non-radiative relaxation pathways that exist toconnect the ground and electronically excited states. Indeed, this property is believedto endow with photostability the fundamental building blocks of life. Much of theunderstanding of the mechanisms by which these heteroaromatic species are renderedphotoresistive has come from the theoretical studies performed by Sobolewski andcoworkers. In this pioneering work, the presence of low-lying singlet B (π*/3s)states that are dissociative with respect to a heteroatom-hydride bond was suggestedas providing highly efficient pathways to conical intersections with the ground statethat could constitute a universal mechanism for ultrafast electronic relaxation.Consequent experimental and theoretical studies have served to both confirm the important role played by B(π*/3s) states in the excited state dynamics ofheteroaromatic species and the wide-range of systems in which this mechanism isprominent. The focus of this work is the photoinduced dynamics of the prototypicalaromatic amine aniline. Through a number of experimental4and theoretical6studies,the electronic spectrum of aniline in the region4.0to6.0eV is known to bedominated by two bands centred at4.35eV and5.39eV, each corresponding toexcitation to one the first two ππ states. Further, a single low-lying B (π*/3s) statehas been identified to exist between these two3p states at an energy of4.6eV by the(2+2) resonance enhanced multiphoton ionisation measurements of Ebata et al.7
Recent experimental studies of the excited state dynamics of aniline have servedto reveal the rich and complex photochemistry of this molecule. Through the use of ofenergy-resolved H (Rydberg) atom photofragment translational spectroscopymeasurements, Ashfold et al.8reasoned that for excitation energies in excess of4.60eV, N-H dissociation via the S2(π*/3s) state occurs, with the dissociation proceedingdiabatically to produce ground state anilino radicals. The timeresolved ion yieldstudies of Montero and co-workers9furnished both short (165fs) and long (tens ofpicoseconds to nanoseconds) timescales for relaxation following excitation in therange4.60to5.17eV. These timescales were attributed, respectively, to dissociationon the S2(π*/3s) surface, and sequential transfer of population to the S2(ππ)) and S0surfaces. Using femtosecond pump-probe velocity map imaging, Stavros et al. reporta timescale of155fs for the formation of both high and low kinetic energy H-atomsfollowing excitation at5.17eV. Further, excitation to the S1(ππ)) state was found tonot result in direct N-H dissociation. Employing time-resolved photoelectron imaging,Fielding and co-workers find that excitation at energies between5.17and5.21eVresults in a time-scale of decay of <100fs.11,12This is attributed to excitation to thesecond, bright (ππ) state followed by ultrafast internal conversion to the ground state.
The alkoxy radicals1are key intermediates during the combustions, especiallythe oxidation of volatile organic compounds (VOC). In the same way, acetaldehydeplays an important role in both clean and polluted atmosphere because of VOCoxidation. Both alkoxy radicals and acetaldehydes are emitted into the tropospherefrom biogenic and anthropogenic sources. CH3O and acetaldehyde are the typicallyalkoxy radicals and aldehyde, so it is significant to study the chemical reaction ofCH3O with acetaldehyde.
The potential energy surface for CH3O and CH3CHO is theoretically researchedat the BMC-QCISD//(U)B3LYP/6-311+G(d,p) level. Three kinds of mechanisms arefound: hydrogen abstraction, addition-elimination andaddition-isomerization-elimination. The addition reaction can be explained by π-πaddition, not nucleophili addition reaction. The TST and multichannelRice–Ramsperger–Kassel–Marcus theory are carried out rate constants fordeterminant channels over a wide range of temperatures and pressures. The major products of the total reaction are CH3CH and CH3OH. The individual rate constant(k1=8.73E-15cm3molecule-1s-1) is good agree with the experiment (8.30E-15cm3molecule-1s-1) at298K. The total rate constant is also in good accordance withexperimental results.
在苯胺激发态动力学方面的研究中，我们首先需要构建模型哈密顿函数，耦合多方面的参数，这里包括了苯胺的六个电子态。采用K ppel等人的二次振动耦合哈密顿算符。这些参数是通过拟合大量的运动方程耦合簇原理，以及双激发的EOM-CCSD方法得到的。在4.0–6.0eV区域进行了吸收光谱的计算和分析。
基于二次振动耦合模型的哈密顿算符用于研究苯胺的电子吸收光谱。拟合了大量的EOM-CCSD计算结果得到模型哈密顿函数的参量。与CASSCF和SAC-CI相比，EOM-CCSD方法得到的结果在第二个ππ*态附近有2个3p里德伯态。采用CR-EOM-CCSD(T)方法得到的结果与EOM-CCSD一致。
采用模型哈密顿函数，波包传播计算了激发到A (ππ*)和B (π*/3s)态的吸收光谱，其中发现A (ππ*)和C (3pz)有强烈的耦合作用。对于A (ππ)光谱，线性偶极激发算符，以及Herzberg-Teller效应的运用显得至关重要。
激发到E (ππ)的光谱，通过模型哈密顿函数能非常好的表示出来。短时动力学研究表明，D (3py)和C (3pz)态表现活跃。但是实验提出的从E (ππ)态到基态的最有可能的路径没有包含在模拟中，因为在模型中没有设置S1/S0交叉点的存在。所以下一步的工作希望能找出更合理的模型势能函数，包含更合理的构型区间。
第二部分研究了甲醛与臭氧的反应机理和动力学性质。
甲醛和臭氧广泛存在于地球表面大气层中。近些年，臭氧机被用来―减少‖室内污染物。然而通过臭氧机与室内不饱和有机物的反应会产生醛类产物，这使得室内污染物并没有减少，反而加大了危害。尽管甲醛和臭氧的反应在很早就开始了研究，但是远没像乙醛与臭氧反应那样受到重视。Li等人开展了用臭氧去除室内甲醛的实验研究，结果发现其反应速率低，效果不佳。
采用BMC-CCSD//BHandHLYP/6-311+G(d,p)方法计算了甲醛(CH2O)和臭氧(O3)在单重态和三重态上的势能面。提出了多条可能的异构化和解离反应路径。在单重态和三重态势能面上均找到了氢提取，氧提取，碳加成消除这三类反应通道。反应的主要通道是通过氢提取过程生成HCO和HOOO。采用过渡态(TST)理论和多通道RRKM理论计算了多个温度和压力下主要通道的反应速率和总速率，反映出温度强依赖和压力弱依赖的性质。
第三部分是乙醛与甲氧基自由基的反应机理和动力学性质的研究。
甲氧基是有机物燃烧的重要中间体，特别是在挥发性有机化合物的氧化过程中，广泛存在。此外，乙醛虽然是一种大气污染物，但也能用来消除空气中部分挥发性有机化合物。不管是生物作用还是人类活动，都大量产生这两种物质。甲氧基作为最小的烷氧基与乙醛这种最典型的醛类反应的研究，有很重要的意义。
采用了密度泛函(B3LYP)理论和从头算电子相关(MP2)方法，结合6-311+G(d,p)基组进行了构型的优化。因MP2方法有较大的自旋污染，且与实验构型比较也没有B3LYP方法好，所以采用了B3LYP优化后的构型。在BMC-QCISD//(U)B3LYP/6-311+G(d,p)水平下进行了势能面的系统研究，发现醛基中的氢提取，生成CH3CO和CH3OH为主反应，与实验结果一致。并得出在298K时的速率常数为8.73E-15cm3molecule-1s-1，与实验结果符合得非常好(8.30E-15cm3molecule-1s-1)。对于形成P3和P4的加成消除反应通道，我们推测不是传统的醛类的亲核加成消除反应，但可以用轨道理论进行解释。中间体IM1通过乙醛的HOMO(π轨道)和甲氧基中的LUMO(π*轨道)加成得到。运用过渡态理论和多通道的RRKM理论，我们发现该体系对温度有强依赖，氢提取对压力没有依赖，加成消除反应对压力有一定的依赖，但是在总速率中所占比率太小，所以总反应对压力是没有依赖的。
Formaldehyde (CH2O) and ozone (O3) are ubiquitous species in the atmosphereand at the surface of the Earth. Formaldehyde is a significant pro-knock additive ofthe methane-base fue and is particularly an important intermediate in the oxidation ofalcohols, ethers, and hydrocarbons in general. Moreover, formaldehyde leads to largeaccumulation in air and final pollution because of the thermodynamic stability.Therefore, it causes an environmental concern, especially influence of indoorformaldehyde on health. In recent years, the use of ozone intentionally produced by anozone generator, has been promoted as a means to―reduce‖the concentration ofindoor pollutants. However, reactions between ozone and certain unsaturated organiccompounds in indoor environments have been shown to generate large amount ofaldehydes, which are more reactive and/or irritating than their precursors. Therefore,the consequences of the emission of formaldehyde have been the object of severalstudies. Though the emissions of formaldehyde are related to the ozone as statedearlier, less attention was paid to the reaction of aldehyde with ozone. The relevantkinetic data are desirable to understand the reaction mechanism, to establish theimpact on the ozone, and perform kinetics modeling for the chemical process ofindoor environments. Li et al. experimentally investigated the ozone on removingindoor formaldehyde, and they found that ozone was not effective in formaldehyderemoval through releasing ozone into the room because of the small rate constant.
Much attention has been paid recently to the photochemistry and photophysics ofsmall heteroaromatic molecules, such as phenols, indoles and pyrroles. Such interesthas been invoked partly due to their being analogues of the chromophores ofbiologically important molecules, including the DNA bases and aromatic amino acids.This class of molecules is remarkable for their low fluorescence quantum yields, aproperty that has it’s origins in efficient non-radiative relaxation pathways that exist toconnect the ground and electronically excited states. Indeed, this property is believedto endow with photostability the fundamental building blocks of life. Much of theunderstanding of the mechanisms by which these heteroaromatic species are renderedphotoresistive has come from the theoretical studies performed by Sobolewski andcoworkers. In this pioneering work, the presence of low-lying singlet B (π*/3s)states that are dissociative with respect to a heteroatom-hydride bond was suggestedas providing highly efficient pathways to conical intersections with the ground statethat could constitute a universal mechanism for ultrafast electronic relaxation.Consequent experimental and theoretical studies have served to both confirm the important role played by B(π*/3s) states in the excited state dynamics ofheteroaromatic species and the wide-range of systems in which this mechanism isprominent. The focus of this work is the photoinduced dynamics of the prototypicalaromatic amine aniline. Through a number of experimental4and theoretical6studies,the electronic spectrum of aniline in the region4.0to6.0eV is known to bedominated by two bands centred at4.35eV and5.39eV, each corresponding toexcitation to one the first two ππ states. Further, a single low-lying B (π*/3s) statehas been identified to exist between these two3p states at an energy of4.6eV by the(2+2) resonance enhanced multiphoton ionisation measurements of Ebata et al.7
Recent experimental studies of the excited state dynamics of aniline have servedto reveal the rich and complex photochemistry of this molecule. Through the use of ofenergy-resolved H (Rydberg) atom photofragment translational spectroscopymeasurements, Ashfold et al.8reasoned that for excitation energies in excess of4.60eV, N-H dissociation via the S2(π*/3s) state occurs, with the dissociation proceedingdiabatically to produce ground state anilino radicals. The timeresolved ion yieldstudies of Montero and co-workers9furnished both short (165fs) and long (tens ofpicoseconds to nanoseconds) timescales for relaxation following excitation in therange4.60to5.17eV. These timescales were attributed, respectively, to dissociationon the S2(π*/3s) surface, and sequential transfer of population to the S2(ππ)) and S0surfaces. Using femtosecond pump-probe velocity map imaging, Stavros et al. reporta timescale of155fs for the formation of both high and low kinetic energy H-atomsfollowing excitation at5.17eV. Further, excitation to the S1(ππ)) state was found tonot result in direct N-H dissociation. Employing time-resolved photoelectron imaging,Fielding and co-workers find that excitation at energies between5.17and5.21eVresults in a time-scale of decay of <100fs.11,12This is attributed to excitation to thesecond, bright (ππ) state followed by ultrafast internal conversion to the ground state.
The alkoxy radicals1are key intermediates during the combustions, especiallythe oxidation of volatile organic compounds (VOC). In the same way, acetaldehydeplays an important role in both clean and polluted atmosphere because of VOCoxidation. Both alkoxy radicals and acetaldehydes are emitted into the tropospherefrom biogenic and anthropogenic sources. CH3O and acetaldehyde are the typicallyalkoxy radicals and aldehyde, so it is significant to study the chemical reaction ofCH3O with acetaldehyde.
The potential energy surface for CH3O and CH3CHO is theoretically researchedat the BMC-QCISD//(U)B3LYP/6-311+G(d,p) level. Three kinds of mechanisms arefound: hydrogen abstraction, addition-elimination andaddition-isomerization-elimination. The addition reaction can be explained by π-πaddition, not nucleophili addition reaction. The TST and multichannelRice–Ramsperger–Kassel–Marcus theory are carried out rate constants fordeterminant channels over a wide range of temperatures and pressures. The major products of the total reaction are CH3CH and CH3OH. The individual rate constant(k1=8.73E-15cm3molecule-1s-1) is good agree with the experiment (8.30E-15cm3molecule-1s-1) at298K. The total rate constant is also in good accordance withexperimental results.
引文
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