Liquid-glass transition as the freezing of characteristic acoustic frequencies

Half-quantum interpretation is proposed for the liquid-glass transition as the freezing of characteristic acoustic frequencies (degrees of freedom) that are related to the molecular mobility of delocalized excited kinetic units, namely, linear quantum oscillators. There exists a correlation between the energy quantum of an elementary excitation (atom delocalization energy) and the glass transition temperature, which is proportional to the characteristic Einstein temperature. By analogy with the Einstein theory of the heat capacity of solids, the temperature range of the concentration of excited atoms in an amorphous medium is divided into the following two regions: a high-temperature region with a linear temperature dependence of this concentration and a low-temperature region, where the concentration of excited atoms decreases exponentially to the limiting minimum value (about 3%). At this value, the viscosity increases to a critical value (about 10¹² Pa s), which corresponds to the glass transition temperature, i.e., the temperature of freezing the mobility of excited kinetic units. The temperature dependence of the free activation energy of viscous flow in the glass transition range is specified by the temperature dependence of the relative number of excited atoms.     

On the role of delocalization of atoms in melting of crystals and softening of glasses

The interrelation between the delocalization of atoms during melting of crystals and their excitation during softening of glasses is considered. The fraction of excited kinetic units (particles displaced through the critical distance) at the softening temperature is close in order of magnitude to the fraction of delocalized atoms at the melting point. The entropy of glass-liquid quasi-phase transition almost coincides with the entropy of melting of crystals with “loose structures.” It is proposed that the elementary acts of crystal melting and glass softening are of the same origin.     

Shear viscosity of glass-forming melts in the liquid-glass transition region

A new approach to interpreting the hole-activation model of a viscous flow of glass-forming liquids is proposed. This model underlies the development of the concept on the exponential temperature dependence of the free energy of activation of a flow within the range of the liquid-glass transition in complete agreement with available experimental data. The “formation of a fluctuation hole” in high-heat glass-forming melts is considered as a small-scale low-activation local deformation of a structural network, i.e., the quasi-lattice necessary for the switching of the valence bond, which is the main elementary event of viscous flow of glasses and their melts. In this sense, the hole formation is a conditioned process. A drastic increase in the activation free energy of viscous flow in the liquid-glass transition region is explained by a structural transformation that is reduced to a limiting local elastic deformation of the structural network, which, in turn, originates from the excitation (critical displacement) of a bridging atom like the oxygen atom in the Si-O-Si bridge. At elevated temperatures, as a rule, a necessary amount of excited bridging atoms (locally deformed regions of the structural network) always exists, and the activation free energy of viscous flow is almost independent of temperature. The hole-activation model is closely connected with a number of well-known models describing the viscous flow of glass-forming liquids (the Avramov-Milchev, Nemilov, Ojovan, and other models).     

Model of delocalized atoms in the physics of the vitreous state

A development of the model of delocalized atoms of liquids and glasses is proposed. It is shown that the basic equation of the model for the probability of delocalization (excitation) of an atom can be obtained not only from the Clausius relation but also by other methods of statistical physics. Techniques for calculating the parameters of the model are developed. The critical displacement of an atom from the equilibrium position, which corresponds to the maximum interatomic attraction force, can be considered as a delocalization (local excitation) of this atom in an elastic continuum. The energy of the critical displacement of an atom calculated as the work of the limit elastic deformation of the interatomic bond in an elastic continuum is in agreement with the results of calculation by the model of delocalized atoms. This energy can also be calculated from the data on surface tension and atomic volume. In silicate glasses, the process of delocalization of an atom represents the critical displacement of a bridging oxygen atom in the structural fragment of a silicon-oxygen (Si-O-Si) network before the switching of the valence bond, whereas, in amorphous organic polymers, the delocalization of an atom corresponds to the limit displacement of a fragment of the main chain of a macromolecule (a group of atoms in the connecting link).     

Relation between elastic modulus and glass softening temperature in the delocalized atom model

The ratio of softening temperature (glass transition temperature) to elastic modulus (T _g /E) is mainly determined by the limiting elastic deformation of an interatomic bond, which characterizes the transition of a structural microregion from an elastic into a viscous-flow state. In silicate glasses, this transition is caused by the limiting deformation of directed ionic-covalent Si-O-Si bonds. In the case of amorphous hydrocarbons, it is related to the relatively weak intermolecular bonds between regions in chain macromolecules, and the T _g /E ratio is significantly higher than in inorganic glasses. In glassy systems of one class, this ratio turns out to be constant (T _g /E ?? const), and a linear correlation is detected between softening temperature and elastic modulus, which can be explained in terms of the delocalized atom model. The values of T _g /E can be used to classify glasses similarly to the well-known Angell classification according to so-called fragility.     

Application of the model of delocalized atoms to metallic glasses

The parameters of the model of delocalized atoms applied to metallic glasses have been calculated using the data on empirical constants of the Vogel–Fulcher–Tammann equation (for the temperature dependence of viscosity). It has been shown that these materials obey the same glass-formation criterion as amorphous organic polymers and inorganic glasses. This fact qualitatively confirms the universality of the main regularities of the liquid–glass transition process for all amorphous materials regardless of their origin. The energy of the delocalization of an atom in metallic glasses, Δε _e ≈ 20–25 kJ/mol, coincides with the results obtained for oxide inorganic glasses. It is substantially lower than the activation energies for a viscous flow and for ion diffusion. The delocalization of an atom (its displacement from the equilibrium position) for amorphous metallic alloys is a low-energy small-scale process similar to that for other glass-like systems.     

Nonradiative transition to the ground state and superelastic scattering of exited atoms upon impact on the surface of wide-bandgap dielectrics

The impact of excited cesium atoms on sapphire and glass surfaces have been experimentally studied. It is established that the probability of electron excitation quenching upon impact of an atom on the dielectric surface is close to unity. The velocity distribution of unexcited atoms upon scattering from the surface has been determined using the time-of-flight technique. The kinetic energies of most of these atoms are several tens of times greater than the energy of thermal motion of the excited atoms impinging on the surface. Conversion of the internal energy of atoms into their kinetic energy is explained in terms of nonradiative electron transitions with simultaneous excitation of lattice vibrations in the dielectric crystal. This mechanism of atomic excitation quenching near the dielectric surface explains the significant difference between the energies of atoms upon superelastic scattering and upon photodesorption from an adsorbed state.     

One method of describing the transfer of energy of the kinetic degrees of freedom to the electronic states of molecules

An analysis is made of the process of transferring the kinetic energy of highly excited vibrational terms of a molecule to an electronic state of one of its constituent atoms. This is done by utilizing a wave equation for the effective wave functions of the atom, corresponding to mixed states, in which the velocity of this atom relative to the neighboring atoms in the molecule enters as a parameter. An expression is found for the excitation probability in the case of a hydroge-like atom in the resonant approximation. State University, Omsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 20–26, September, 1996.     

强耦合腔-QED系统中原子的纳秒脉冲激发光谱研究

本文在多原子强耦合腔-QED系统中,利用脉冲宽度为5 ns的强脉冲光在垂直于腔轴方向直接激发原子,脉冲的峰值功率为40 mW,通过光学腔观测激发原子辐射到腔中的光子获得相应的激发光谱。我们发现当光场频率和原子跃迁失谐±80 MHz时原子激发率达到最大,而在共振时原子激发被抑制。我们建立了脉冲光与三能级原子相互作用的模型,通过缀饰态能够解释此现象。     

重复频率脉冲大气放电中氮气的振动温度

氮气分子的振动自由度在大气放电低温等离子体中会被高度激发。从振动能级的简谐振子模型和Boltzmann分布近似出发,研究重复频率脉冲放电中振动温度的变化行为。结果表明,决定重频条件下振动温度的主要过程是电子碰撞振动激发和振动-平动弛豫,而在振动能级高度激发的情形下其与氧原子的化学反应也会产生影响。对于振动激发过程,通过跃迁反比相似率推导出的特征弛豫时间与动理学模型符合较好。在振动-平动弛豫中占主导贡献的为干燥大气中的氧原子或潮湿大气中的水分子。当氧原子数密度为1014 cm-3时,若初始振动温度在5000 K,在化学反应过程中振动能量的特征弛豫时间在0.1~1 s量级。     

Phase transitions in simple clusters

Formation of the liquid state of clusters with pairwise interactions between atoms is examined within the framework of the void model, in which configurational excitation of atoms results from formation of voids. Void parameters are found from computer simulation by molecular dynamics methods for Lennard-Jones clusters. From that standpoint, phase transitions are analyzed in terms of two aggregate states. This information allows us to divide the entropy jump during a solid-liquid phase transition into two parts: one corresponds to configurational excitation at zero temperature and the other arises from thermal vibrations of atoms. The latter part contributes approximately 40% for Lennard-Jones clusters consisting of 13 and 55 atoms, increasing to 56% for bulk inert gases. These magnitudes explain the validity of melting criteria based on thermal motion of atoms, even though the distinctive mechanism of this phase transition results from configurational excitations. It is shown that the void concept allows analyzing various aspects of the liquid state of clusters including the existence of a limiting freezing temperature below which no metastable liquid state exists, as well as the existence and properties of glassy states that may exist below the freezing limit.     

Optical field-induced mass transport in As2S3 chalcogenide glasses

We report the observation of a photorefractivelike nonlinearity responsible for the formation of giant relief modulations in amorphous semiconductor glasses. The photoinduced softening of the matrix, formation of defects with enhanced polarizability, and their drift under the optical field gradient force is believed to be the origin of the mass transport.     

Cobmecтhaя диффuзия фop;oh;ob и khcy;acтиц b пoлuБecкoheчhom пpocтpahcтbe—I pacпpeдeлehиe boзБuждehhьч aтomob b пoлuБecкoheчhom пpocтpahcтbe

The excited atom distribution produced by the simultaneous action process, namely, excitation transfer by radiation in a spectral line and spce movement of excited atoms, is considered. A kinetic equation describing these process is analysed. For steady-state conditions, an adympototic analytical solutio id obtained. This solution describes the concentration distribution of excited atoms for a plane geometry in a region which is a distance exceeding the effective free path away from the surface limiting the volume.The influence on the general solution of either the excitation transfer process id found as a function of the parameters involved.     

基于缠结微结构的非晶态玻璃态高分子材料屈服行为的分子动力学研究

非晶态玻璃态高分子材料作为结构材料在工程领域应用广泛,其机械力学性能特别是屈服变形行为受到热处理、加载应变率和环境温度的影响.采用分子动力学模拟方法研究非晶态玻璃态高分子材料不同工况下的单轴拉伸变形,基于分子链缠结微结构的概念,阐明了非晶态玻璃态高分子材料屈服和应变软化过程的内在变形机制.结果表明,拓扑缠结具有较为稳定的空间结构,难以发生解缠,决定了非晶态高分子材料屈服后的软化平台.由相邻分子链的局部链段相互作用形成的次级缠结在一定外界条件下可发生破坏或重新生成,次级缠结微结构及其演化是非晶态高分子材料发生屈服及软化的内在物理原因.     

Magnetic-field control of subradiance states of a system of two atoms

A method is proposed for the creation of an entangled metastable (subradiance) excited state in a system of two closely spaced identical atoms. The system of unexcited atoms is first placed in a magnetic field that is directed at a magic angle of \({\alpha _0} = {\text{arccos}}\left( {1/\sqrt 3 } \right) \approx 54.7^\circ \) to the line connecting the atoms and has a transverse gradient. The gradient of the field results in the detuning of frequencies of an optical transition of the atoms. Then, the resonant laser excitation of an atom with a higher transition frequency is performed with the subsequent adiabatic switching-off of the gradient of the magnetic field. It is shown that the excited atomic system in this case transits with overwhelming probability to an entangled subradiance state. Requirements on the spectroscopic parameters of the transitions and on the rate of varying the gradient of the magnetic field necessary for the implementation of this effect are analyzed.     

Excited atoms in argon gas discharge plasma

General principles are discussed for a gas discharge plasma involving excited atoms where electron-atom collision processes dominate. It is shown that an optimal kinetic model of this plasma at not large electric field strengths can be based on the rate constants of quenching excited atom states by electron impact. The self-consistent character of atom excitation in gas discharge plasma is important and results in the tail of the energy distribution function of electrons being affected by the excitation process, which in turn influences the excitation rate. These principles are applied to an argon gas discharge plasma where excitation and ionization processes have a stepwise character and proceed via formation of argon atom states with the electron shell 3p ⁵4s.     

The limits of the rotating wave approximation in electromagnetic field propagation in a cavity

We consider three two-level atoms inside a one-dimensional cavity, interacting with the electromagnetic field in the rotating wave approximation (RWA). One of the three atoms is initially excited, and the other two are in their ground state. We numerically calculate the propagation of the field emitted by the excited atom and scattered by the second atom, as well as the excitation probability of the second and third atom. Our numerical results clearly show the limits of the RWA in subtle problems such as relativistic causality in the atom–field interaction.     

超冷里德堡原子的产生以及探测

利用激光冷却与俘获技术获得冷原子,由双光子激发产生超冷里德堡原子,利用场电离法得到了里德堡原子ns和nd态的离子谱图;再将激光波长固定在6p3/2-34d态的共振跃迁线上,得到了离子和里德堡原子的TOF(Time of Flight)图,并对实验结果做了分析.     

非晶合金的离子辐照效应

非晶合金作为一种快速凝固形成的新型合金材料,引起了材料研究者的极大兴趣.微观结构上长程无序、短程有序的特征使其具有独特的物理、化学和力学性能,在许多领域展现出良好的应用前景,尤其是有望成为核反应堆、航空航天等强辐照环境下的备选结构材料.本文深入探讨非晶合金的辐照效应,主要讨论离子辐照对非晶合金微观结构、宏观力学性能以及其他物理化学性能的影响,可为进一步理解非晶合金的微观结构和宏观力学性能之间的关系提供有效的实验和理论基础,也可为非晶合金在强辐照环境下的服役性能预测提供实验依据,对推进非晶合金这一先进材料的工程化应用具有重要的理论与实际意义.     

Inelastic electron collisions with Rydberg atoms

The standard classical method of computer simulation is used for evaluation of the inelastic cross section in electron collisions with a highly excited (Rydberg) atom. In the course of collision, the incident and bound electrons move along classical trajectories in the Coulomb field of the nucleus, and the scattering parameters are averaged over many initial conditions. The reduced ionization cross section of a Rydberg atom by electron impact approximately corresponds to that of atoms in the ground states with valence s-electrons and coincides with the results of the previous Monte Carlo calculations. The cross section of an atom transition between Rydberg atom states as a result of electron impact is used for finding the stepwise ionization rate constant of atoms in collisions with electrons or the rate constant of three-body electron-ion recombination in a dense ionized gas because these processes are determined by kinetics of highly excited atom states. Surprisingly, the low-temperature limit of electron temperatures is realized when the electron thermal energy is lower than the atom ionization potential by about three orders of magnitude, as follows from the kinetics of excited atom states. The article is published in the original.