共查询到19条相似文献,搜索用时 93 毫秒
1.
2.
3.
铁基高温变换催化剂制备的穆斯堡尔谱研究──I.铁氧化物前驱态的相变过程 总被引:1,自引:0,他引:1
用穆斯堡尔诺及XRD技术对不同铁氧化物前驱态的相变过程进行了研究.FeCO3沉淀在空气中老化时被氧化分解生成FeO(OH),经干燥、煅烧后全部转化为α-Fe2O3Fe(OH)2沉淀物在空气中老化时则转化为FeaO4·2H2O和FeOOH,并且两者的相对含量受Fe2+的迁移速度和Fe(OH)2的氧化速度的影响.干燥、煅烧后,Fe3O4·2H2O转化生成γ-Fe2O3,FeOOH则转化生成α-Fe2O3,由此所得铁氧化物的晶型是可以调节的. 相似文献
4.
5.
6.
CH2F2…H2O中强π型二级氢键 总被引:1,自引:3,他引:1
通过从头计算,用较大基组6-311+G(2d,2p),在MP2水平上计算得到CH2F2…H2O体系的优化几何构型,与实验结构一致.其中∠F…H-O=116.5°,偏离普通氢键之键角达到63.5°.为探讨产生氢键巨大弯曲的原因,采用点电荷扫描的办法,探测CH2F2…H2O体系中H2O的O原子上的两对孤电子对的方向,发现了一个强的π型二级氢键相互作用.使用这种新的相互作用方式说明了产生这一巨大氢键弯曲的原因,并且在MP4水平上使用Counterpoise技术计算了π型二级氢键的稳定化能. 相似文献
7.
8.
利用从头算和RRKM理论研究了一氟二氯代甲烷热解离动力学,并得到了一套热力学和动力学参数。研究了三种不同的解离通道:(1)HCl+CFCl_2,(2)Cl+CHFCl,(3)HF+CCl_2,它们的活化能分别为:243.3、258.9、309.8kJ/mol。研究结果表明,氯化氢消除反应和碳氯键简单断键反应是两个主要的并且是竞争的通道,三个反应通道的高压速率常数分别为k_1=8.74×10~(14)exp(-29163T)_s~(-1),k_2=7.09×10~(15)exp(-31121/T)_s~(-1),R_3=3.87×10~(11)exp(-37039/T)_s~(-1),它们都具有明显的温度和压力依赖关系。 相似文献
9.
10.
通过等摩尔竞争反应研究了氟化物催化的硅氢化合物和取代酚的脱氢偶联反应机理。研究表明,p-XC6H4OH在反应中的取代基效应与氟化物催化取代苯甲醛p-XC6H4CHO的硅氢化反应中的不同,这表明它们的反应机理存在差异,在这两种反应中,虽然F^-对Si的配位都促进了硅氢化合物中的H对底物中带正电荷原子的亲核进攻,但是在催化酚解反应中,由于没有四中心过渡态的形成,因此下一步取代酚中的氧原子对F^-配位的 相似文献
11.
12.
To understand the effect of different vibrational and rotational modes of reactant to enhance the reactivity of the O + HO2 → OH + O2 reaction, we revisited this important atmospheric reaction. We report here a quasi-classical trajectory (QCT) study of the reaction dynamics on a recently developed full-dimensional potential energy surface (PES). Our previous work has indicated that this reaction has two pathways, the H abstraction (HA) channel and the O abstraction (OA) channel, which lead to totally different product energy distribution. In this work, we identified that the vibrational excitation of the OH stretching (v1) mode of HO2 is the switch of the HA channel at low collision energy; meanwhile, the rotational excitation can also greatly change the branching ratio of the two pathways. With the excitation of v1 mode, the original negligible HA channel controlled by the tight transition state becomes quite important. This work presents an approach to control the branching ratio via collaboration between vibrational and rotational excitation and will enrich the knowledge of the O + HO2 reaction in atmospheric chemistry and physics. 相似文献
13.
14.
Results of quasiclassical trajectory calculations of reactive processes between He atoms and H2+ (υ, J) molecular ions in the collision energy interval 0.5–5.0 eV (c.m.) for a large number of selected υ, J combinations are analyzed with respect to the influence of the initial translational, vibrational, and rotational energy on the total and differential reaction cross sections. Vibrational energy is more effective in promoting the reaction than translational energy. Small rotational excitation has a negligible effect, whereas high rotational excitation has a similar influence on the reaction cross sections as the vibrational excitation of the same magnitude. 相似文献
15.
The product CH radical of the subject reaction was monitored by laser-induced fluorescence following vacuum ultraviolet photolysis of C3O2. As expected from consideration of reaction energetics, only the ground vibrational level was observed. The rotational population distribution in CH(ν″ = 0) matches well a calculated RRHO prior distribution which is averaged over a 300 K Boltzmann distribution of available reactant energy. The experimental results are compared to rotational population distributions derived from previously reported classical trajectory calculations. 相似文献
16.
The dynamics of the NH + H→N+H2 reaction has been investigated by means of the 3D quasiclassical trajectory approach by using the LEPS potential energy surface.The calculated rate coefficient is in good agreement with the experimental value.The reaction was found to occur via a direct channel.The product H2 has a cold excitation of rotational state,but has a reverse distribution of the vibrational state with a peak at v=1.Based on the potential energy surface and the trajectory analysis,the reaction mechanism has been explained successfully. 相似文献
17.
The application of centrifugal and rotational sudden approximations to classical trajectory studies of rotational energy transfer in atom—molecule collisions to examined. Two different types of approximations are considered: a centrifugal sudden (CS) approximation, in which the orbital angular momentum is assumed to be constant during collisions, and a classical infinite order sudden (CIOS) approximation, in which the CS treatment is combined with an energy sudden approximation to totally decouple translational and rotational equations of motion. The treatment of both atom plus linear and nonlinear molecule collisions is described, including the use of rotational action-angle variables for the rotor equations of motion. Applications of both CS and CIOS approaches to rotational energy transfer in He + I2 collisions are presented. We find the calculated CS and CIOS rotationally inelastic cross sections are in generally good agreement [errors of (typically) 10–50%] with accurate quasiclassical (QC) ones, with the CS results slightly more accurate than CIOS. Both methods are less accurate for small |Δj| transitions than for large |Δj| transitions. Computational savings for the CS and CIOS applications is about a factor of 3 (per trajectory) compared to QC. We also present applications using the CS method to rotational energy transfer in He, Ar, Xe + O3 collisions, making comparisons with analogous QC results of Stace and Murrell (SM). The agreement between exact and approximate results in these applications is generally excellent, both for the average energy transfer at fixed impact parameters, and for rotationally inelastic cross sections. Results are better for He + O3 and Ar + O3 than for Xe + O3, and better at low temperatures than at high. Since SM's quasiclassical treatment considered only total internal energy transfer without attempting a partitioning between vibration and rotation, while our CS calculation considers only rotational energy transfer, the observed good agreement between our and SM's cross sections indicates that most internal energy transfer in He, Ar, Xe + O3 is rotational. The relation of this result to models of the activation process in thermal unimolecular rate constant determination is discussed. 相似文献
18.
V. N. Atasie 《化学物理学报(中文版)》2010,23(5):570-572
The quasi-classical trajectory calculations based on extended London-Eyring-Polanyi-Sato potential energy surface have been used to study the reaction of Ba+HI→BaI+H system. The rotational, vibrational, translational, and angular distributions of the product BaI have been calculated. The calculated results are in good agreement with the experimental ones. 相似文献
19.
The quasi-classical trajectory calculation for the reaction O(1D)+HD is carried out based on the Dobbyn and Knowles potential energy surface. In this work, the reaction cross section and product branching ratio are obtained. The product branching ratio OD/OH was discussed. The calculated results show that the cross-section decreases thoroughly with the increasing of the collision energy from 4.6 kJ/mol to 46.0 kJ/mol. The average branching ratio decrease with the increase of rotational quantum number of reactant HD. 相似文献