共查询到20条相似文献,搜索用时 1 毫秒
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We theoretically study the dissociation of H2+ by UV laser pulses as a function of the photon energy ω of the pulse. Our results show that pronounced enhancements of the dissociation into highly excited electronic states can be achieved at some critical ω. This is found to be attributed to a consecutively resonant excitation mechanism where the population is first transferred to the first excited state by absorbing one photon and then to higher states by absorbing another one or more photons at the same internuclear distance. This study indicates that the strong coupling between the lowest two states of H2+ can significantly affect the dissociation through higher lying states. 相似文献
3.
A general method for controlling dynamical system to various desired goal dynamics is proposed. The convergent condition of the coptrol is suggested analytically.A technique of introducing "traasient" goal allows the control to be switched on at any time, and the system quickly conforms to the goal closely,almost without transient, resulting in only very small perturbations to the system parameter. The effciency and superiority of the method is illusrated by simulations on logistic map and Henon map. This method enables dynamical system to operate in a much wider variety of situations than that originally desgned. 相似文献
4.
通过研究HOCl分子高激发振动态的动力学势, 明确了该体系的动力学特点. 研究表明, 在O-Cl伸缩模式和H-O-Cl弯曲模式间存在2:1 Fermi共振的动力学模型下, H-O伸缩振动模式对于上述两种振动模式的动力学势有显著影响, 且这种影响随Polyad数呈现有规律的变化. 作为定量研究, 还研究了Polyad数为24时该分子体系的动力学势与各能级的相空间轨迹. 分析表明, 相空间轨迹与动力学势中的动力学不动点有很好的对应关系. 此外, 将该Polyad数下的动力学势中的能级按照相空间轨迹的作用量积分进行分类, 明确了这些能级所处的量子环境. 相似文献
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In this paper the equilibrium structure of HCO has been optimized by using density functional theory (DFT)/ B3P86 method and CC-PVTZ basis. It has a bent (Cs, X^2A') ground state structure with an angle of 124.4095 °. The vibronic frequencies and force constants have also been calculated. Based on the principles of atomic and molecular reaction statics, the possible electronic states and reasonable dissociation limits for the ground state of HCO molecule have been determined. The analytic potential energy function of HCO (X^2A') molecule has been derived by using the many-body expansion theory. The contour lines are constructed, which show the static properties of HCO (X^2A'), such as the equilibrium structure, the lowest energies, etc. The potential energy surface of HCO (X^2A') is reasonable and very satisfactory. 相似文献
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Global dynamical analysis of vibrational manifolds of HOCl and HOBr under anharmonicity and Fermi resonance: the dynamical potential approach 下载免费PDF全文
The vibrational dynamics of HOCl and HOBr between
bending and OCl/OBr stretching coordinates with anharmonicity and
Fermi coupling is studied with the classical dynamical potential
approach. The quantal vibrational dynamics is mostly mapped out by
the classical nonlinear variables such as fixed points, except for
the state energies, which are quantized. This approach is global in
the sense that the focus is on a set of levels instead of individual
ones. The dynamics of HOBr is demonstrated to be less complicated.
The localized modes along the OCl/OBr stretching coordinates are
also shown to have O--Br bonds more prone to dissociation. 相似文献
7.
Global dynamical analysis of vibrational manifolds of HOCl and HOBr under anharmonicity and Fermi resonance:the dynamical potential approach 下载免费PDF全文
The vibrational dynamics of HOCl and HOBr between bending and OCl/OBr stretching coordinates with anharmonicity and Fermi coupling is studied with the classical dynamical potential approach. The quantal vibrational dynamics is mostly mapped out by the classical nonlinear variables such as fixed points, except for the state energies, which are quantized. This approach is global in the sense that the focus is on a set of levels instead of individual ones. The dynamics of HOBr is demonstrated to be less complicated. The localized modes along the OCl/OBr stretching coordinates are also shown to have O-Br bonds more prone to dissociation. 相似文献
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Ab initio calculations of accurate dissociation energy and analytic potential energy function for the second excited state B1∏ of 7LiH 下载免费PDF全文
The reasonable dissociation limit of the second excited singlet state
B1∏ of 7LiH molecule is obtained. The accurate dissociation energy and
equilibrium geometry of the B1\Pi state are calculated using a
symmetry-adapted-cluster configuration--interaction method in full active space. The
whole potential energy curve for the B1∏ state is obtained over the
internuclear distance ranging from about 0.10nm to 0.54nm, and has a least-square
fit to the analytic Murrell--Sorbie function form. The vertical excitation energy is
calculated from the ground state to the
B1∏ state and compared with previous theoretical results. The
equilibrium internuclear distance obtained by geometry optimization is found to be
quite different from that obtained by single-point energy scanning under the same
calculation condition. Based on the analytic potential energy function, the harmonic
frequency value of the B1∏ state is estimated. A comparison of the
theoretical calculations of dissociation energies, equilibrium interatomic distances
and the analytic potential energy function with those obtained by previous
theoretical results clearly shows that the present work is more comprehensive and in
better agreement with experiments than previous theories, thus it is an improvement
on previous theories. 相似文献
9.
本文考虑等离子体密度分布变化, 得到了修正屏蔽库仑势的解析解. 数值分析以及分子动力学模拟表明, 在常见实验室参数情况下, 等离子体密度分布变化引起的屏蔽库仑势修正对二维尘埃等离 子体系统的动力学和结构特性影响很小. 在极限参数情况下, 本模型的计算结果表明二维尘埃等离子体系统的扩散能力明显降低, 并且系统组态呈圆形分布. 此外, 本文还研究了实验室常见大小磁场对二维尘埃等离子体系统的影响.
关键词:
修正屏蔽库仑势
二维尘埃等离子体
分子动力学模拟 相似文献
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Emerging of Stochastic Dynamical Equalities and Steady State Thermodynamics from Darwinian Dynamics 总被引:1,自引:0,他引:1
The evolutionary dynamics first conceived by Darwin and Wallace, referring to as Darwinian dynamics in the present paper, has been found to be universally valid in biology. The statistical mechanics and thermodynamics, while enormous successful in physics, have been in an awkward situation of wanting a consistent dynamical understanding. Here we present from a formal point of view an exploration of the connection between thermodynamics and Darwinian dynamics and a few related topics. We first show that the stochasticity in Darwinian dynamics implies the existence temperature, hence the canonical distribution of Boltzmann-Gibbs type. In term of relative entropy the Second Law of thermodynamics is dynamically demonstrated without detailed balance condition, and is valid regardless of size of the system. In particular, the dynamical component responsible for breaking detailed balance condition does not contribute to the change of the relative entropy. Two types of stochastic dynamical equalities of current interest are explicitly discussed in the present approach: One is based on Feynman-Kac formula and another is a generalization of Einstein relation. Both are directly accessible to experimental tests. Our demonstration indicates that Darwinian dynamics represents logically a simple and straightforward starting point for statistical mechanics and thermodynamics and is complementary to and consistent with conservative dynamics that dominates the physical sciences. Present exploration suggests the existence of a unified stochastic dynamical framework both near and far from equilibrium. 相似文献
12.
Fabio Martinelli 《Journal of statistical physics》1992,66(5-6):1245-1276
We present results on the Swendsen-Wang dynamics for the Ising ferromagnet in the low-temperature case without external field in the thermodynamic limit. We discuss in particular the rate of convergence to the equilibrium Gibbs state in finite and infinite volume, the absence of ergodicity in the infinite volume, and the long-time behavior of the probability distribution of the dynamics for various starting configurations. Our results are purely dynamical in nature in the sense that we never use the reversibility of the process with respect to the Gibbs state, and they apply to a stochastic particle system withnon- Gibbsian invariant measure. 相似文献
13.
含能材料中键离解能的密度泛函理论计算 总被引:3,自引:2,他引:1
通过计算一个包括臭氧,硝基甲烷以及1,3,5 -三硝基-1,3,5-三氮杂环已烷(RDX)在内的典型系统的键离解能,对由四种交换/相关函数(BLYP,B3LYP,B3PW91和B3P86)加上不同的基函数组合而成的多种密度泛函方法的准确性进行了比较研究.结果表明:B3P86/6-31G**是计算该系统C-NO2,O-O和N-NO2键离解能的最可靠的方法. 相似文献
14.
We present an investigation of the optical properties of semiconductors, which are excited by a strong laser pulse. On the basis of a nonequilibrium Green's function technique (Keldysh formalism) we study the system of electrons and holes, interacting among themselves and with the exciting pulse. A set of coupled equations for the one-particle Green's function and the transverse and longitudinal polarizability is derived, which is valid for arbitrary excitation conditions. For an initially prepared state, which is not too far from a quasiequilibrium state of the excited system, the theory is elaborated in detail, using a screened Hartree-Fock approximation scheme. Within this approximation earlier results of various theoretical approaches are found to be special cases of the equilibrium limit of the present theory. 相似文献
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采用密度泛函理论方法对聚对苯二甲酸丁二醇酯(PBT)二聚体的键离能进行了计算.为了选取较为精确的方法来计算PBT各个键的键离能,以与PBT具有相同的酯基官能团的乙酸乙酯为模型参照物.采用M062X, B3P86, M06, PBE0, wB97xD方法分别在基组6-31G(d), 6-311G(d), 6-311+G(d, p), 6-311++G(d, p), cc-pVDZ, cc-pVTZ水平下对乙酸乙酯的键离能进行计算.通过对比计算结果与iBonD数据库的乙酸乙酯实验测定值可知,M062X在基组6-311G(d)水平下计算结果与实验值最为接近.因此,本研究采用M062X方法在基组6-311G(d)水平下对聚对苯二甲酸丁二醇酯(PBT)二聚体的键离能进行计算.计算结果表明:在PBT的各键中C-Carcmatic键的键离能最大,主链上的C-C键离能最小,为370.9 kJ/mol.其次就是C-O键,为404.6 kJ/mol.基于PBT键离能的计算结果,设计了3条PBT二聚体热降解过程可能形成的反应路径,分析了热解产物的形成机理.结果表明PBT二聚体热解过程可... 相似文献
16.
Bending localization of nitrous oxide under anharmonicity and Fermi coupling: the dynamical potential approach 下载免费PDF全文
This paper studies the vibrational nonlinear dynamics of nitrous oxide with Fermi coupling between the symmetric stretching and bending coordinates by classical dynamical potential approach.This is a global approach in the sense that the overall dynamics is evidenced by the classical nonlinear variables such as the fixed points and the focus are on a set of levels instead of individual ones.The dynamics of nitrous oxide is demonstrated to be not so much dependent on the excitation energy.Moreover,the localized bending mode is shown to be ubiquitous in all the energy range studied. 相似文献
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A. Chernomoretz C. O. Dorso 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,24(1-3):197-202
In this communication we analyze the behavior of excited
drops that undergo fragmentation. We focus our attention on two
scenarios: in the first one the system is free to expand, while
in the second one it is confined inside a spherical volume. It
is shown that the caloric curve of free expanding systems does
not display a vapor branch. In the case of constrained ones,
they behave as undergoing a first order phase transition at low
densities while as a second order one at high densities. The
transition from liquid-like to vapor-like behavior is signaled
both by the caloric curves and thermal response functions. 相似文献
19.
三硝基甲烷键离解能和生成焓的理论计算 总被引:5,自引:0,他引:5
采用密度泛函(DFT)四种交换/相关函数(B3LYP、B3P86、B3PW91和PBE0)结合不同的基函数,求得了三硝基甲烷C-NO2键的离解能(BDE),并且通过合理选择参考物硝基甲烷,设计等键等电子对反应,计算了气相三硝基甲烷分子的生成焓(HOF).与实验数据进行比较,PBE0/6-31g*计算出的BDE值最好,误差为-2.1 kcal mol-1;PBE0密度泛函结合带极化函数的6-31g基组得到的HOF值与实验值吻合的最好(误差在0.1 kcal mol-1以内). 相似文献
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Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids 下载免费PDF全文
Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies(BDEs) for 15 acids.These compounds are studied by utilizing the hybrid density functional theory(DFT)(B3LYP,B3PW91,B3P86,PBE1PBE) and the complete basis set(CBS-Q) method in conjunction with the 6311G** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed. 相似文献