用量子力学方法计算H+H2碰撞的反应几率

利用量子力学耦合通道扭曲波近似法(CCDWA)和三种势能面计算了H+H2碰撞的反应几率,结果发现在相同的势能面下利用CCDWA方法计算的反应几率和公认较好的计算结果符合很好,不同势能面共线势垒高度的差别将引起反应几率的不同.     

重离子裂变反应中的能级密度参数和裂变几率

本工作从Nilsson单粒子能级入手，计算了形变核^186Os、^187Ir、^189Os和^193Au作为激发函数的固有能级密度参数aint和有效能级密度参数（包括核集体运动效应）aelf，由这样能量相关的能级密度参数计算的理裂几率Pf（U）与本工作的裂变几率符合很好。     

Na＋I2→Na^＋＋I^—2离子对生成反应几率的LCAC—SW量子散射计算

将ＬＣＡＣ－ＳＷ方法推广到离子对生成反应的动力学研究,导出了计算态－态反应几率的理论公式,并在Ａｔｅｎ－Ｌａｎｔｉｎ－Ｌｏｓ两态势能面上计算得到了Ｎａ＋Ｉ２→Ｎａ＾＋＋Ｉ＾－２电离反应的共线选态反应几率,结果表明反应几率随碰撞能增加呈振荡变化,该反应阈能约为２．８ｅＶ,与实验值相近。     

用LCAC—SW法计算H＋H2（0）→H2＋H一维共线反应几率

用排列通道线性组合散射波方法计算了一维共线反应Ｈ＋Ｈ２（０）→Ｈ２＋ＪＨ的反应几率。在采用较小基组的情况下，得到了与精确量子计算数值相吻合的结果。     

SiH4+H→H2+SiH3反应的约化维数计算

对SiH4+ H→H2+SiH3反应体系应用SVRT模型进行了4维的量子动力学计算.将得到的速率常数与实验数据以及其他理论方法进行比较,得出了一些有意义的结论,并与CH4+H→H2+CH3反应在同种理论模型下做了对比,较好的与实验相吻合.最后验证了理论方法以及势能面的正确性.     

用精确的量子力学方法研究N + OD反应的动力学性质

采用close coupling (CC)方法,在3A’’势能面上[Guadagnini R, Schatz G C, Walch S P. Global potential energy surface for the lowest 1A’, 3A’’, and 1A’’ states of HNO [J]. J. Chem. Phys., 1995,10:774],我们利用量子含时波包方法对N + OH的同位素反应—N + OD进行了研究。在0.0-0.8 eV的平动能范围内,选态的反应几率受共振结构支配。利用 -shifting方法计算,我们得到了基态的速率常数,并对分子间的同位素效应进行了研究。     

重离子裂变反应中的能级密厦参数和裂变几率

本工作从Ｎｉｌｓｓｏｎ单粒子能级入手,计算了形变核１８６Ｏｓ、１８７Ｉｒ、１８９Ｏｓ和１９３Ａｕ作为激发函数的固有能级密度参数ａｉｎｔ和有效能级密度参数（包括核集体运动效应）ａｅｆｆ．由这样能量相关的能级密度参数计算的裂变几率Ｐｆ（Ｕ）与本工作的裂变几率符合很好． Based on the single-particle levels given by Nilsson,the intrinsic and effective(with collective effects)level density parameters as a function of theexcitation energy for the 186Os, 187Ir, 189Os and 193Au deformation nuclei have been calculatedin the range of the excitation energy up to 150MeV. The calculated fission probabilities Pf(U) are consistent satisfactorily with the experimental data when a nonadiabtic estimation ofthe collective effects was used to calculate the nuclear level density parameters.     

原子-多原子分子反应的含时波包理论研究

基于Modified Jordan和Gilbert的势能面，运用SVRT(semirigid vibrating rotor target)模型和TDWP(Time-Dependent Wave Packet)方法，对D CH4，O(^3P) CH4反应体系进行了含时波包动力学研究，计算得到了不同初始振动态的总反应几率，总散射截面和热速率常数。通过对j=0时，v=0，1的反应几率的计算，看出H—CH3的振动激发，极大地提高了反应几率，而反应阈能明显降低，说明反应分子的振动能对分子的碰撞反应有重要贡献。     

原子-多原子分子反应的含时波包理论研究

基于Modified Jordan和Gilbert的势能面,运用SVRT(semirigid vibrating rotor target)模型和TDWP(Time-Dependent Wave Packet)方法,对D+CH4,O(3P)+CH4反应体系进行了含时波包动力学研究,计算得到了不同初始振动态的总反应几率,总散射截面和热速率常数.通过对j=0时,v=0,1的反应几率的计算,看出H-CH3的振动激发,极大地提高了反应几率,而反应阈能明显降低,说明反应分子的振动能对分子的碰撞反应有重要贡献.     

基于珠串分子动力学的漫游反应H+MgH的反应速率研究

本文使用珠串分子动力学计算了多通道漫游反应H+MgH→Mg+H₂的热速率系数,明确考虑了两个反应通道：紧致和漫游通道. 首次将珠串分子动力学方法应用于多通道反应. 借助新开发的方法,即用于准备初始结构的优化插值工具和自适应的力常数选择方法,成功获得了热速率系数. 本文结果与其他理论方法,如变分过渡态理论和量子动力学结果一致. 珠串分子动力学速率结果显示出速率对温度的负相关性,这与变分过渡态理论的结果相似,但与基态量子动力学的结果不同.     

基于双核模型的粒子交换势能面与熔合几率的研究(英文)

研究了基于双核模型的粒子交换势能面.原子核的形变效应对于势能面的形状有较大的影响.在反应过程中,作为反应时间函数的动态形变的变化是显著的.通过求解主方程,对一些基于冷熔合机制的反应道的全熔合几率也进行了讨论. The Potential Energy Surface (PES) for particle exchange in Di nuclear system is studied in detail. It is found that the nuclear deformation effect can change the shape of PES significantly. The dynamical deformation as a function of the reaction time in the reaction process is investigated in a simple model and we found that its variation with time is dramatic. The fusion probabilities P-CN of some reaction channels based on the mechanism of cold fusion are also calculated.     

量子非欧姆阻尼环境中的重核熔合概率及热核裂变速率

考虑处于量子非欧姆阻尼环境下的重核熔合及热核裂变系统的动力学,给出了数值模拟相应c数量子广义朗之万方程的方法。其中提出的产生任意关联量子色噪声的数值方法,适用于任意非马尔科夫过程噪声的产生。利用此方法计算了重核熔合概率,结果表明量子涨落对重核熔合具有“低抬高压”的效应:当粒子的初始动能小于（大于）临界初始动能时,量子涨落会增大（减小）粒子鞍点通过概率。非欧姆阻尼环境中粒子稳定通过概率随δ值的变化是非单调的,且当粒子初始动能小于（大于）临界初始动能,量子涨落会使稳定通过概率随δ值变化曲线的极大值位置向右（向左）漂移。此外,在热核裂变系统中,超欧姆阻尼环境会增大裂变速率,而量子涨落不仅显著增大裂变速率,还使裂变速率随δ值变化曲线的极大值位置发生漂移。Dynamics of heavy-ion fusion and nuclear fission system in a quantum non-Ohmic environment have been considered and a numerical simulation method to solve the corresponding c-number quantum generalized Langevin equation is proposed. The method of generating quantum colored noise with arbitrary correlation can be applied to generate noise of arbitrary non-Markov process. Calculating fusion probability of heavy nuclei with this method, the result has shown that the passing probability is enlarged (decreased) by the quantum fluctuation when the initial kinetic energy of the particle is less than (greater than) the critical initial kinetic energy. Steady passing probability of particle in non-Ohmic environment versus is nonmonotonic. Quantum fluctuation makes the maximum position of the curve drift towards right (left), when the initial kinetic energy of the particle is less than (greater than) the critical initial kinetic energy. Furthermore, nuclear fission rate is larger in super-Ohmic environment. Quantum fluctuation enlarges nuclear fission rate and makes the the maximum position of nuclear fission rate versus δ drift.     

Probability Metrics and Uniqueness of the Solution to the Boltzmann Equation for a Maxwell Gas

We consider a metric for probability densities with finite variance on ^d , and compare it with other metrics. We use it for several applications both in probability and in kinetic theory. The main application in kinetic theory is a uniqueness result for the solution of the spatially homogeneous Boltzmann equation for a gas of true Maxwell molecules.     

Theoretical Study on Mechanism of Reaction of OH with HO2NO2

运用密度泛函的B3LYP方法及CBS-QB3方法对HO2NO2(过氧硝酸,PNA)与OH自由基的反应进行了理论研究. 结果表明, 在计算所得的势能面曲线上存在五个产物通道,分别为H2O+NO2+O2、HOOH+NO3、NO2+HO3H、HO2+HONO2和HO2+HOONO. 对这五个通道分别进行了详细的研究,其中最主要的反应通道为：PNA+OH!M1!TS1!H2O+NO2+O2. 采用了一个准平衡近似的方法并运用CBS-QB3基础上的能量计算得到了300K下此反应路径的速率常数值为1.13 ￡10-1     

2-巯基苯并咪唑螯合棉纤维对重金属离子的吸附速率方程

以预处理后的棉纤维为骨架，通过间接醚化法，接枝合成了2－巯基苯半螯合棉纤维（CC－MBM），研究了CC－MBM吸附重金属离子的动力学行为。实验表明，CC－MBM吸附速率快，吸附平衡时间短，吸附量随时间的变化规律遵从Langmuir方程。     

(1+2+1)双共振多光子电离概率的理论研究

共振增强多光子电离光谱技术已成为研究原子、分子高激发态能级结构的重要方法。运用光和物质相互作用的速率方程理论,推导出四能级物质系统1+2+1双共振增强多光子电离概率的解析表达式,以此为基础,理论模拟了电离概率随激发光强、激光脉冲宽度和碰撞弛豫速率的变化,发现在1+2+1多光子电离机制中,电离概率随光强的增加而增大,继而出现单步、双步激发饱和的现象,直至饱和值1;继续增大光强,电离概率将围绕饱和值1窄幅振荡,振荡幅度随光强增加而增大。随激光脉冲宽度的增大,电离概率从零开始逐渐增大直至饱和值1。而随碰撞弛豫速率的增大电离概率以线性规律减小。     

Master Equation and Fokker–Planck Equation: Comparison of Entropy and of Rate Constants

A usual approximation of the master equation is provided by the Fokker–Planck equation. For chemical systems with one species, we prove generally that the prediction of the rate constant of the metastable state given by the Master equation and the Fokker–Planck approximation differ exponentially with respect to the size of the system. We show that this is related to the fact that the entropy of the metastable state is not described correctly by the Fokker–Planck equation. We prove that the rate given by the Fokker–Planck equation overestimates that rate given by the Master equation.     

Necessity of Exact Calculation for Transition Probability

This paper shows that exact calculation for transition probability can make some systems deviate fromFermi golden rule seriously. This paper also shows that the corresponding exact calculation of hopping rate inducedby phonons for deuteron in Pd-D system with the many-body electron screening, proposed by Ichimaru, can explainthe experimental fact observed in Pd-D system, and predicts that perfection and low-dimension of Pd lattice are veryimportant for the phonon-induced hopping rate enhancement in Pd-D system.     

CH3与NO2的反应

用时间分辨傅立叶红外光谱法和量子化学计算，研究了CH3自由基与NO2的基元反应．由248 nm激光光解CH3Br或CH3I得到CH3自由基．首次观测到了振动激发的产物OH、HNO和CO2．另一产物NO也被证实．由此确定了反应通道CH3O+NO，CH2NO+OH 和HNO+H2CO．其中CH3O+NO是主要的反应通道．还用CCSD(T)/6-311++G(df,p)//MP2/6-311G(d,p)的方法对上述通道的机理在理论上做了研究．理论计算的结果与实验观察相符．