OClO与OH反应机理的理论研究

用密度泛函B3LYP/-311+G~(* *)和级电子相关倒映 合簇CCSD(T)/6-311+G~(* *)方法研究了OClO与OH反应的微观机理，研究结果表明：该反应经过缔合、H转移 和离解等复杂过程，最终得到四种产物，分别为HOCl+O_2，HCl+O_3,ClO+HO_2和 HOClO_2,从能量上看，形成HOCl+O_2和HCl+O_3的通道更容易进行，而形成 ClO+HO_2的通首在动力学上是最不利的。     

CH_3O与CIO双自由基反应机理的量子化学研究

在QCISD(T)/6-311+G(d,p)//B3LYP/6-311+G(3df,3pd)水平上,对CH3O与ClO双自由基反应进行了理论研究.结果表明,该反应共有三个反应通道,产物分别为HOCI+CH2O,CH2O2+HCl和CH3Cl+O2(1△).不论从动力学角度,还是从热力学角度看,形成产物HOCl+CH2O的通道均是最有利的,因此为主要反应通道,这与实验观察到的结果是一致的.     

NCS自由基与NO反应动力学的理论研究

用量子化学密度泛函理论B3LYP/6-31+G*和高级电子相关校正的偶合簇[CCSD(T)/6-311+G*]方法,对NCS自由基与NO反应的机理和动力学进行了理论研究,得到了体系的势能面信息和可能的反应机理.计算了反应的热力学参数及反应能垒.采用传统过渡态理论计算了各反应通道的速率常数.研究结果表明,NCS自由基与NO反应中存在4个反应通道,产物分别为OCS+N2,CS+N2O,ONS+CN和ONCNS.从能量变化和反应速率两方面考虑,NCS+NOOCS+N2应为主反应通道.     

CH3O与ClO双自由基反应机理的量子化学研究

在QCISD(T)/6-311＋G(d,p)//B3LYP/6-311＋G(3df,3pd)水平上, 对CH₃O与ClO双自由基反应进行了理论研究. 结果表明, 该反应共有三个反应通道, 产物分别为HOCl＋CH₂O, CH₂O₂＋HCl和CH₃Cl＋O₂(¹Δ). 不论从动力学角度, 还是从热力学角度看, 形成产物HOCl＋CH₂O的通道均是最有利的, 因此为主要反应通道, 这与实验观察到的结果是一致的.     

C_2h_3自由基与O_2反应机理的量子化学研究

用量子化学从头计算中UMP2(full)方法优化了C_2H_3自由基与O_2反应通道上 驻点（反应物、中间体、过渡态和产物）的几何构型，在Gaussian-3(G3)水平上计 算了它们的能量。在此基础上计算了该反应通道上各基元反应的反应活化能。通过 我们的研究发现，C_2H_3自由基与氧气反应存在着三元环、四元环和五元环反应机 理，且分别生成不同的产物，从反应活化能的计算结果扯CH_2O和CHO是反应的主要 产物，其次还可能生成CH_3 + CO_2, CH_2CO_2 + H, C_2H_2 + O_2H和COHCOH + H等产物，且它们生成几率逐渐减少，我们对生成产物CH_2O + CHO, CH_3 + CO_2, C_2H_2 + O_2H和COHCOH + H四条反应通道化学反应热的计算结果与实验吻 合较好。     

CH3SS与OH自由基反应机理的理论研究

应用密度泛函理论(DFT)对CH3SS与OH自由基单重态反应机理进行了研究.在B3PW91/6-311+G(d,p)水平上优化了反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型,用内禀反应坐标(IRC)计算和频率分析方法对过渡态进行了验证.在QCISD(T)/6-311++G(d,p)水平上计算了各物种的单点能,并对总能量进行了零点能校正.研究结果表明,CH3SS与OH反应为多通道反应,有5条可能的反应通道.反应物首先通过不同的S—O键相互作用形成具有竞争反应机理的中间体IM1和IM2.再经过氢迁移、脱氢和裂解等机理得到主要产物P1(CH2SS+H2O),次要产物P2(CH2S+HSOH),P3(CH3SH+1SO)和P4(CH2SSO+H2),其中最低反应通道的势垒为174.6kJ.mol-1.     

CH~2(^3B~1)+H~2→CH~3+H的反应途径及动态理论研究

用从头算的UHF/6-31G方法,反应途径哈密顿理论以及变分过渡态理论, 计算了反应CH~2(^3B~1)+H~2→CH~3+H的反应途径.沿反应途径的动态学性质和正则变分过渡态理论的速率常数,用变分过渡态方法处理效果明显;较低温度下考虑隧道效应更重要,而用小曲率近似的校正是有效的;H~2 分子的振动激发对反应速率常数有较大增进.     

CH~2(^3B~1)+H~2→CH~3+H的反应途径及动态理论研究

用从头算的UHF/6-31G方法,反应途径哈密顿理论以及变分过渡态理论, 计算了反应CH~2(^3B~1)+H~2→CH~3+H的反应途径.沿反应途径的动态学性质和正则变分过渡态理论的速率常数,用变分过渡态方法处理效果明显;较低温度下考虑隧道效应更重要,而用小曲率近似的校正是有效的;H~2 分子的振动激发对反应速率常数有较大增进.     

CH3O与ClO双自由基反应机理的量子化学研究

在QCISD(T)／6—311 G(d,p)／／B3LYP／6．311 G(3df,3pd)水平上,对CH3O与CIO自由基反应进行了理论研究．结果表明,该反应共有三个反应通道,产物分别为HOCI CH2O,CH2O HCl和CH3CI O2(1△)．不论从动力学角度,还是从热力学角度看,形成产物HOCl CH2O的通道均是最有利的,因此为主要反应通道,这与实验观察到的结果是一致的．     

CH3CH2,CH3CHCl,CH3CCl2与NO2反应微观动力学理论研究

运用量子化学密度泛函理论UB3LYP/6-311+G*和高级电子相关校正的偶合簇(CCSD(T)/6-311+G*)方法,对CH3CH2,CH3CHCl和CH3CCl2自由基与NO2反应的机理和动力学进行了理论研究,得到了体系的势能面信息和可能的反应机理.根据计算得到的各反应热力学参数及反应能垒,采用传统过渡态理论计算了各反应在温度T=298 K和T=700 K时的速率常数.研究结果表明,该类反应均通过1个中间体和1个过渡态生成产物,产物分别为CH3CHO+HNO,CH3CHO+ClNO和CH3CClO+ClNO.     

Ab initio study of the reaction path of the reaction HNCO+CN

HNCO is a convenient photolytic source of NCO and NH radicals for laboratory kinetics studies of elementary reaction[1] and plays an important role in the combustion and atmosphere chemistry. It can re- move deleterious compounds rapidly from exhausted ga…     

H＋CH2CO反应机理的G2计算

分别在UQCISD/6-311G(d,p)和G2理论计算水平上，对CH2CO和H反应可能存在的四条反应通道进行了研究，详细分析了每个通道的反应机理;通过振动分析的虚频数和内禀反应坐标(IRC)计算,确认了反应涉及的每一个过渡态.通过反应位能剖面的比较，发现经过一个中间体生成CH3＋CO的一条途径是主反应通道，该通道是个放热反应，总焓变为－146.07 kJ•mol－1，速控步骤的位垒为55.09 kJ•mol－1.理论计算结果较好地解释了实验观察到的主要产物和副产物并存的现象。     

(H_2O)_n(n=0～2)催化HS和HOCl反应机理的理论研究

在CCSD(T)/6-311+G(3df,2p)//M06-2X/6-311+G(3df,2p)水平上研究了(H_2O)n(n=0~2)催化HS和HOCl的反应机理.结果表明,HS与HOCl反应中HS夺取HOCl上的H原子形成产物H_2S和ClO.在无水催化时,该反应存在2种不同的路径(分别经过过渡态TS1和TS2,二者互为顺反结构),对应的能垒分别为100.28和100.91kJ/mol,到达产物(H_2S+ClO)需吸收18.99kJ/mol能量,反应不易发生;在单个水分子参与时,水分子可通过形成弱相互作用或者作为H原子转移桥梁影响反应机理,获得了4种水催化路径,能垒(间于53.97~92.39kJ/mol之间)均低于无水催化过程.同时发现,在反应到达产物前,水分子可以与产物形成中间体IM,IM相对能仅为0.46kJ/mol,有利于产物形成;有2个水分子参与反应时,找到了3条催化路径,最优反应路径过渡态TS7的能垒为45.05kJ/mol,低于无水催化过程,相比单个水分子最优路径能垒(53.97kJ/mol)并无显著降低.     

Ab initio/density functional theory and multichannel RRKM study for the ClO + CH2O reaction

The potential energy surface for the CH(2)O + ClO reaction was calculated at the QCISD(T)/6-311G(2d,2p)//B3LYP/6-311G(d,p) level of theory. The rate constants for the lower barrier reaction channels producing HOCl + HCO, H atom, OCH(2)OCl, cis-HC(O)OCl and trans-HC(O)OCl have been calculated by TST and multichannel RRKM theory. Over the temperature range of 200-2000 K, the overall rate constants were k(200-2000K) = 1.19 x 10(-13)T(0.79) exp(-3000.00/T). At 250 K, the calculated overall rate constant was 5.80 x 10(-17) cm(3) molecule(-1) s(-1), which was in good agreement with the experimental upper limit data. The calculated results demonstrated that the formation of HOCl + HCO was the dominant reaction channel and was exothermic by 9.7 kcal/mol with a barrier of 5.0 kcal/mol. When it retrograded to the reactants CH(2)O + ClO, an energy barrier of 14.7 kcal/mol is required. Furthermore, when HOCl decomposed into H + ClO, the energy required was 93.3 kcal/mol. These results suggest that the decomposition in both the forward and backward directions for HOCl would be difficult in the ground electronic state.     

Direct dynamic study on the hydrogen abstraction reaction of H2CO with NCO

A direct ab initio dynamics method is used to investigate the hydrogen‐abstraction reaction of H₂CO with NCO. The potential energy surface information is obtained at the MP2/6‐311G(d,p) level. More accurate single‐point energy is refined at the G3(MP2)//MP2/6‐311G(d,p) level. Furthermore, the rate constants of reaction H₂CO + NCO are evaluated by using the canonical variational transition state theory with small‐curvature tunneling contributions over a wide temperature range of 200–2000 K. The calculated reaction enthalpy and rate constants are in good agreement with the available experimental values. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 394–400, 2009     

Theoretical study of the mechanism of CH2CO + CN reaction

The potential energy surface information of the CH₂CO + CN reaction is obtained at the B3LYP/6‐311+G(d,p) level. To gain further mechanistic knowledge, higher‐level single‐point calculations for the stationary points are performed at the QCISD(T)/6‐311++G(d,p) level. The CH₂CO + CN reaction proceeds through four possible mechanisms: direct hydrogen abstraction, olefinic carbon addition–elimination, carbonyl carbon addition–elimination, and side oxygen addition–elimination. Our calculations demonstrate that R→IM1→TS3→P3: CH₂CN + CO is the energetically favorable channel; however, channel R→IM2→TS4→P4: CH₂NC + CO is considerably competitive, especially as the temperature increases (R, IM, TS, and P represent reactant, intermediate, transition state, and product, respectively). The present study may be helpful in probing the mechanism of the CH₂CO + CN reaction. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Kinetics of the OH + ClOOCl and OH + Cl2O reactions: experiment and theory

The rate coefficients for the reactions OH + ClOOCl --> HOCl + ClOO (eq 5) and OH + Cl2O --> HOCl + ClO (eq 6) were measured using a fast flow reactor coupled with molecular beam quadrupole mass spectrometry. OH was detected using resonance fluorescence at 309 nm. The measured Arrhenius expressions for these reactions are k5 = (6.0 +/- 3.5) x 10(-13) exp((670 +/- 230)/T) cm(3) molecule(-1) s(-1) and k6 = (5.1 +/- 1.5) x 10(-12) exp((100 +/- 92)/T) cm(3) molecule(-1) s(-1), respectively, where the uncertainties are reported at the 2sigma level. Investigation of the OH + ClOOCl potential energy surface using high level ab initio calculations indicates that the reaction occurs via a chlorine abstraction from ClOOCl by the OH radical. The lowest energy pathway is calculated to proceed through a weak ClOOCl-OH prereactive complex that is bound by 2.6 kcal mol(-1) and leads to ClOO and HOCl products. The transition state to product formation is calculated to be 0.59 kcal mol(-1) above the reactant energy level. Inclusion of the OH + ClOOCl rate data into an atmospheric model indicates that this reaction contributes more than 15% to ClOOCl loss during twilight conditions in the Arctic stratosphere. Reducing the rate of ClOOCl photolysis, as indicated by a recent re-examination of the ClOOCl UV absorption spectrum, increases the contribution of the OH + ClOOCl reaction to polar stratospheric loss of ClOOCl.     

Computational study of the deamination reaction of cytosine with H2O and OH-

The mechanism for the deamination reaction of cytosine with H(2)O and OH(-) to produce uracil was investigated using ab initio calculations. Optimized geometries of reactants, transition states, intermediates, and products were determined at RHF/6-31G(d), MP2/6-31G(d), and B3LYP/6-31G(d) levels and for anions at the B3LYP/6-31+G(d) level. Single-point energies were also determined at B3LYP/6-31+G(d), MP2/GTMP2Large, and G3MP2 levels of theory. Thermodynamic properties (DeltaE, DeltaH, and DeltaG), activation energies, enthalpies, and free energies of activation were calculated for each reaction pathway that was investigated. Intrinsic reaction coordinate analysis was performed to characterize the transition states on the potential energy surface. Two pathways for deamination with H(2)O were found, a five-step mechanism (pathway A) and a two-step mechanism (pathway B). The activation energy for the rate-determining steps, the formation of the tetrahedral intermediate for pathway A and the formation of the uracil tautomer for pathway B, are 221.3 and 260.3 kJ/mol, respectively, at the G3MP2 level of theory. The deamination reaction by either pathway is therefore unlikely because of the high barriers that are involved. Two pathways for deamination with OH(-) were also found, and both of them are five-step mechanisms. Pathways C and D produce an initial tetrahedral intermediate by adding H(2)O to deprotonated cytosine which then undergoes three conformational changes. The final intermediate dissociates to product via a 1-3 proton shift. Deamination with OH(-), through pathway C, resulted in the lowest activation energy, 148.0 kJ/mol, at the G3MP2 level of theory.     

Reaction of hypochlorous acid with imidazole: formation of 2-chloro- and 2-oxoimidazoles

Reaction of hypochlorous acid (HOCl) with imidazole (Im) taken as a model for the 5-membered ring of guanine, leading to the products 2-chloro- and 2-oxo-imidazoles was investigated at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels of density functional theory. For all cases, single point energy calculations were performed at the MP2/AUG-cc-pVDZ level of theory using the geometries optimised at the B3LYP/AUG-cc-pVDZ level. Intrinsic reaction coordinate calculations were performed to ensure genuineness of all the calculated transition states. Effect of aqueous media was investigated by solvating all the species involved in the reactions using the polarizable continuum model. It is found that 2-chloroimidazole (2-ClIm) can be formed following three different reaction schemes while 2-oxoimidazole (2-oxoIm) can be formed following two different reaction schemes. The calculated barrier energies show that formation of 2-oxoIm would be less favored than that of 2-ClIm, which explains the experimental observations on relative yields of 8-chlorodeoxyguanosine and 8-oxodeoxyguanosine.