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1.
利用CCSD(T)和MP2的理论方法研究了OH与臭氧反应,并考虑大气中水分子的影响.理论计算探索了OH与臭氧反应的两个反应通道,计算出的能垒与以前的实验和理论符合得较好.当水分子被加入时,反应变得更加复杂,发现了六个反应通道,更重要的是反应能垒降低约4.18 kJ/mol.为了评估这些过程在大气化学中的重要作用,用过渡态理论计算了反应速率.计算结果表明,在298 K,对于没有水参加反应的反应速率为5.16×10-14 cm3/(molecule s)与实验一致.  相似文献   

2.
采用M06-2X和CCSD(T)高阶量化计算和传统过渡态理论研究硫酸催化乙二醛气体相水化反应.对HCOCHO+H2O, HCOCHO+H2O+H2O, HCOCHO+H2O+H2O, HCOCHO+H2O...H2SO4和HCOCHO+H2O+H2SO4五个路径的反应机理和速率常数进行了研究.计算结果表明硫酸具有较强的催化能力,能显著减小乙二醛水化反应的能垒,在CCSD(T)/6-311++G(3df,3pd)//M06-2X/6-311++G(3df,3pd)理论水平,当硫酸分子参与乙二醛水化反应时,反应能垒从37.15 kcal/mol减少至7.08 kcal/mol.在室温条件下,硫酸催化乙二醛水化反应的反应速率1.34×10-11 cm3/(molecule.s),是等量水分子参与乙二醛水化反应的速率的1012倍,大于乙二醛与OH自由基反应的反应速率1.10×10-11 cm3/(molecule.s).这表明大气条件下,硫酸催化乙二醛水化反应可以发生,同乙二醛与OH自由基反应相竞争.  相似文献   

3.
根据最新的Cs2分子中间态A1+u -b3Πu全局解微扰获得的能级数据, 归属了通过微扰增强红外-红外光学双共振中间态A1+u 到上态231g的140条碰撞线, 包含之前实验观测到的221条231g←A1+u← X1+g 双共振跃迁[J. Chem. Phys. 128, 204313 (2008)], 重新计算了231g态的分子常数和势能曲线(排除54个微扰能级). 本次拟合得到的离心畸变常数和从经验公式计算得到的值相符合. 在亚多普勒激发光谱中,没有分辨出231g态的超精细结构. 对231g态的超精细结构进行初步计算,比较实验结果给出解释和说明.  相似文献   

4.
本文使用OH激光诱导荧光方法研究了结构最简单的克里奇中间体CH2OO和CF3CF=CF2的反应动力学. 在压强为10 Torr条件下,测量了温度在283,298,308和318 K的反应速率常数,分别为(1.45±0.14)×10-13,(1.18±0.11)×10-13,(1.11±0.08)×10-13和(1.04±0.08)×10-13 cm3·molecule-1·s-1. 根据阿伦尼乌斯方程,获得该反应的活化能为(-1.66±0.21) kcal/mol. 在6.3∽70 torr压力范围内,未观察到该反应的速率常数存在压力相关.  相似文献   

5.
用时间分辨傅立叶变换红外发射光谱(TR-FTIR)和G3MP2//B3LYP/6-311G(d,p)水平的电子结构计算研究了环境化学中重要的二氯代乙烯自由基C2HCl2和O2分子的基元反应通道和机理. 通过0.5 cm-1高分辨的TR-FTIR发射光谱观察到三种振动激发态产物CO2、CO和HCl,由光谱拟合得到CO和HCl的振动态分布,结合电子结构计算的反应势能曲线,提出反应机理和能量上最可能的反  相似文献   

6.
用密度泛函理论B3LYP方法和6-311G(d,p)/Lanl2DZ优化得到黄曲霉素B1(AFB1)分子及其复合物AFB1-Ag的稳定结构,并计算了复合物的表面增强拉曼光谱和预共振拉曼光谱. 结果表明,AFB1分子的拉曼光谱很大程度依赖于吸附位点以及入射光的激发波长. 与分子的常规拉曼光谱相比,复合物表面增强拉曼光谱中C=O伸缩振动模的增强因子约为102~103复合物的极化率增强而导致的静态化学增强,并分析了振动模式的振动方向与其拉曼强度的关系.选择复合物最大吸收峰附近激发光266和482 nm以及远离共振吸收波长785和1064 nm作为入射光,计算得到不同入射光激发下复合物的预共振拉曼光谱.结果表明其增强因子最大达到104量级,主要是由电荷转移产生的共振增强引起的.  相似文献   

7.
分别在水、甲酸和硫酸存在的情况下,通过CCSD(T)//M06-2X/6-311++G(3df,3pd)的理论方法,对大气中自由基OH提取甲酰氟FCHO上的氢进行了反应机理和动力学的研究.计算结果表明相对于反应物,加入催化剂的过渡态的能垒从3.64 kcal/mol分别下降到-2.89、-6.25和-7.76 kcal/mol,表明水、甲酸和硫酸在甲酰氟FCHO和自由基OH提氢反应中起了重要作用.通过运用具有Eckart隧道校正的传统过渡态理论计算出的动力学数据表明通道X...FCHO+OH(X=H2O, HCOOH,或者H2SO4)要比通道X...OH+FCHO更有利于反应的发生.催化剂水、甲酸和硫酸的加入使甲酰氟FCHO 和自由基OH提氢反应的速率常数要比不加催化剂时小,说明了催化剂的加入不能促进大气中甲酰氟FCHO和自由基OH的反应.  相似文献   

8.
研究氢抽取反应OH+H2S对于理解酸雨形成、空气污染和气候变化的原因具有重要意义. 本文在降维模型下使用量子含时波包方法研究了OH+H2S→H2O+SH反应的动力学行为. 研究表明,该反应在低碰撞能时表现出无垒反应的特征,而在高碰撞能下表现出具有显著势垒的激活反应的特征. 激发反应物H2S分子的对称或反对称伸缩模式比激发弯曲模式更有效地促进了反应,该动力学特征可以通过各正则模式与反应坐标的耦合强度来解释. 此外,模式指定的反应速率常数表现出明显的非阿伦尼乌斯温度依赖性.  相似文献   

9.
用从头算方法的MP2和CCSD(T)方法结合cc-pVTZ基组计算了二氯化锗同位素(70GeCl272GeCl276GeCl2)分子的平衡结构、光谱常数和非谐振力场.二氯化锗的几何结构、转动常数、振转相互作用常数、谐频、非谐振常数、四次和六次离心畸变常数、三次和四次力常数的计算结果与实验结果符合较好,二氯化锗分子的同位素效应较小,可能的原因是Ge同位素的质量变化相对较小.两种方法计算的结果均与实验结果符合,但CCSD(T)方法比MP2计算结果的偏差稍大一些,可能的原因是CCSD(T)方法在描述过共价Cl原子的电子相关时不够充分.  相似文献   

10.
采用光腔衰荡光谱记录了465-555 nm范围内PH2自由基在射流冷却条件下的吸收光谱. 在超声射流条件下对氩载气中的PH3和SF6混合物直流放电产生PH2自由基. 得到了7个有精细转动结构的振转谱带,并归属为PH2自由基?2A1- Χ2B1电子跃迁的000、2n0、2n1 (n=1-3)跃迁. 在已有的基础上,重新归属每一个振转谱带的转动量子数和转动项值;进一步精细化转动常数、离心畸变常数和自旋转动相互作用常数. 另外还简单讨论了每个K结构受到其它电子态的微扰.  相似文献   

11.
Mechanism and kinetics of NH2OH + OOH and NH2CH3 + OOH reactions were studied at the B3LYP and M062X levels of theory using the 6-311++G(3df, 3pd) basis set. The NH2OH + OOH and NH2CH3 + OOH reactions proceed through different paths which lead to different products. Transition state structure and activation energy of each path were calculated. The calculated activation energies of hydrogen abstraction reactions were smaller than 25 kcal/mol and of substitution reactions are in the range of 50–70 kcal/mol. The rate constants were calculated using transition state theory (TST) modified for tunneling effect at 273–2000 K.  相似文献   

12.
Theoretical investigation has been carried out on the mechanism, kinetics and thermochemistry of the gas-phase reactions between CHF2CF2OCH2CF3 and OH radical using a new hybrid density functional M06-2X/6-31+G(d,p) and G2(MP2)//M06-2X/6-31+G(d,p) methods. The most stable conformer of CHF2CF2OCH2CF3 is considered in our study and the possible H-abstraction reaction channels are identified. Each reaction channel shows an indirect H-abstraction reaction mechanism via the formation of pre-reactive complex. The rate coefficients are determined for the first time over a wide range of temperature 250–1000 K. At 298 K, the calculated total rate coefficient of kOH = 1.01×10?14 cm3 molecule?1 s?1 is in good agreement with the experimental results. The heats of formation for CHF2CF2OCH2CF3 and CF2CF2OCH2CF3 and CHF2CF2OCHCF3 radicals are estimated to be -1739.25, -1512.93 and -1523.94 kJ mol?1, respectively. The bond dissociation energies of the two C-H bonds are C(-H)F2CF2OCH2CF3: 423.34 kJ mol?1 and CHF2CF2OC(-H)HCF3: 411.87 kJ mol?1. The atmospheric lifetime of CHF2CF2OCH2CF3 is estimated to be around 4.5 years and the 100-year time horizon global warming potentials of CHF2CF2OCH2CF3 relative to CO2 is estimated to be 601.  相似文献   

13.
The effects of substituents on the stability of 3‐substituted(X) bicyclo[1.1.1]pent‐1‐yl cations (3) and 4‐substituted(X) bicyclo[2.2.1]hept‐1‐yl cations (4), for a set of substituents (X = H, NO2, CN, NC, CF3, CHO, COOH , F, Cl, HO, NH2, CH3, SiH3, Si(CH3)3, Li, O?, and NH3+) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6‐311 + G(2d,p) and B3LYP/6‐31 + G (d) levels of theory, respectively. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 3/4 and polar field/group electronegativity substituent constants (σF and σχ, respectively). The analysis reveals that the ΔE values for both systems are best described by a combination of both substituent constants. The result highlights the importance of the σχ dependency of charge delocalization in these systems. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

14.
Bifurcated fluorine bond (BFB) interactions are studied in model binary complexes pairing N-formyl formamide derivatives and FX molecules (X = F, CN, NC, CF3 and CCH) by means of ab initio calculations. The calculated F···O binding distances in these complexes are in the range of 2.813–3.048 Å. The corresponding interaction energies lie in a narrow range, from?2.25 to ?16.49 kJ/mol. The nature of BFBs is analysed by a vast number of methods including molecular electrostatic potential, quantum theory of atoms in molecules, non-covalent interaction index and natural bond orbital methods. According to the energy decomposition analysis, the electrostatic and dispersion effects have a dominant role in the formation of these complexes. The formation of a hydrogen- and lithium-bonding interaction tends to increase the strength of BFBs in the ternary XF:NFF-H:NH3 and XF:NFF-Li:NH3 complexes, respectively.  相似文献   

15.
First-principles calculations based on density functional theory (DFT) have been performed to study the adsorption and decomposition of NH3 on Ni(110). The adsorption sites, the adsorption energies, the transition states and the activation energies of the stepwise dehydrogenation of NH3 and the associative desorption of N are determined, and the zero point energy correction is included, which makes it possible to compute the rate constants of the elementary steps in NH3 decomposition. Combined DFT calculations and kinetic analysis at 350 K indicate that the associative desorption of N has a reaction rate lower than NHx dehydrogenation and is therefore the rate determining step. The distinctly different rate constants over Ni(110), Ni(111) and Ni(211) imply that ammonia decomposition over Ni-based catalyst is a structure-sensitive reaction.  相似文献   

16.
In the present investigation, the reaction mechanism and kinetics of 2-formylcinnamaldehyde (2-FC) with O3 and hydroxyl OH radicals were studied. The reaction of 2-FC with O3 radical are initiated by the formation of primary ozonide, whereas the reaction of 2-FC with the hydroxyl OH radical are initiated by two different ways: (1). H-atom abstraction by hydroxyl OH radical from the –CHO and –CH = CHCHO group of 2-FC (2). Hydroxyl OH addition to the –CH = CHCHO group to the ring-opened 2-FC. These reactions lead to the formation of an alkyl radical. The reaction pathways corresponding to the reactions between 2-FC with O3 and hydroxyl OH radicals have been analysed using density functionals of B3LYP and M06-2X level of methods with the 6-31+G(d,p) basis set. Single-point energy calculations for the most favourable reactive species are determined by B3LYP/6-311++G(d,p) and CCSD(T)/6-31+G(d,p) levels of theory. From the obtained results, the hydroxyl OH addition at C8 position of 2-FC are most favourable than the C9 position of 2-FC. The subsequent reactions of the alkyl radicals, formed from the hydroxyl OH addition at C8 position, are analysed in detail. The individual and overall rate constant for the most favourable reactions are calculated by canonical variational transition theory with small-curvature tunnelling corrections over the temperature range of 278–350 K. The calculated theoretical rate constants are in good agreement with the available experimental data. The Arrhenius plot of the rate constants with the temperature are fitted and the atmospheric lifetimes of the 2-FC with hydroxyl OH radical reaction in the troposphere calculate for the first time, which can be applied to the study on the atmospheric implications. The condensed Fukui function has been verified for the most favourable reaction sites. This study can be regarded as an attempt to investigate the O3-initiated and hydroxyl OH-initiated reaction mechanisms of 2-FC in the atmosphere.  相似文献   

17.
ABSTRACT

Structural and thermodynamic properties of 48 trimolecular clusters containing one radicl and two protic molecules (H2O, NH3, H2O2, CH3OH, HOCl) were studied at B3LYP/6-311++G(3df,3pd) level of theory. These radical-clusters have non-cyclic structures and are stabilised via two inter-molecular hydrogen bonding interactions. The calculated enthalpies of formation of the radical-clusters were generally in the range of ?30 to ?50 kJ/mol. The calculated activation energies (Ea) of the intra-cluster hydrogen transfers were smaller than 70 kJ/mol. Also, structures and thermodynamics of 15 cyclic molecular clusters as well as multi-hydrogen transfers in them were investigated. The results showed that the stability of the cyclic clusters and activation energies of the multi-hydrogen transfers depend on the cluster size.  相似文献   

18.
The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.  相似文献   

19.
Reactions between CH3NHNH2 and OOH radical were studied using computational methods. The activation energies (Ea) and Gibbs free energies of activation (ΔG#) were calculated at the MP2 and B3LYP levels of theory. The calculated activation energies of the hydrogen abstraction reactions were less than 100 kJ/mol and those for the substitution reactions were about 150–250 kJ/mol. The calculated activation energies for the intra-molecular hydrogen transfer reactions in CH3NHNH, CH2NNH2 and CH3NN molecules were 210–250 kJ/mol. Catalytic effect of the water molecule on the intra-molecular hydrogen transfer reactions was studied. It was found that the water molecule decreases the activation energies by about 70–100 kJ/mol. Rate constants of the reactions were calculated using transition state theory in the temperature range of 298–2000 K. Consecutive hydrogen abstraction reactions from CH3NHNH2 led to the formation of CH2NN, which was a very stable molecule.  相似文献   

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