Equipartition of rotational and translational energy in a dense granular gas

Experiments quantifying the rotational and translational motion of particles in a dense, driven, 2D granular gas floating on an air table reveal that kinetic energy is divided equally between the two translational and one rotational degrees of freedom. This equipartition persists when the particle properties, confining pressure, packing density, or spatial ordering are changed. While the translational velocity distributions are the same for both large and small particles, the angular velocity distributions scale with the particle radius. The probability distributions of all particle velocities have approximately exponential tails. Additionally, we find that the system can be described with a granular Boyle's law with a van?der?Waals-like equation of state. These results demonstrate ways in which conventional statistical mechanics can unexpectedly apply to nonequilibrium systems.     

Effect of a single quantum rotational excitation on state-to-state dynamics of the O(1D)+H2-->OH+H reaction

Crossed molecular beams scattering experiments on the O(1D)+H2 reaction have been carried out in order to study the effect of the reagent (H2) rotational excitation on the detailed dynamics of this benchmark insertion reation. Experimental results indicate that a single quantum rotational excitation of H2 has a significant impact on the product state distributions at the forward and backward scattering directions, while very little effect has been found in the sideway scattering direction. No clear patterns of this effect are found in the OH-product state distributions, indicating that the single quantum excitation on the dynamics is rather complicated.     

Rovibrational excitation within the infinite conical well: Desorption of diatomic molecules

An analytic model for the hindered rotational states of a diatomic molecule adsorbed upright on a solid surface is discussed. Various model dynamics situations, within the sudden approximation, designed to simulate desorption are presented and rotational state distributions are calculated including both rotational and translational degrees of freedom. Criteria are established for observing rotationally cool desorbed molecules.     

Rotational and vibrational excitation of sputtered diatomic molecules

The rotational and vibrational level population distributions of ground and electronically excited states of several homonuclear and heteronuclear molecules are calculated for direct ejection, association, and associative ionization mechanisms of molecule sputtering. The cascade properties, formation mechanism, initial atom separation, and axis orientation to the surface are clearly reflected in the sputtered molecule distributions. In general, extensive non-Boltzmann rotational and vibrational distributions are predicted. The probability that an atom pair survives the ejection, for typical sputtering parameters, is high; approximately 50% for homonuclear molecules to near 100% for hydrides. The predictions are compared with experimental optical emission spectra in the accompanying paper.     

甲基自由基在212.5 nm的光分解:母体内能态的激发对产物态分布的影响

利用里德堡氢原子飞渡时间谱的方法,进行了甲基自由基在212.5nm 的光解动力学的实验研究.甲基自由基来自于碘甲烷分子在266nm 的光分解.实验测量了不同振动态的甲基自由基通过3s 电子激发态解离的产物 CH_2自由基的平动能分布和角分布,并从平动能分布得到了 CH_2自由基的转动布居.实验同时详细地研究了母体分子甲基自由基的振动和转动激发对光解动力学的影响.实验结果表明母体分乙甲基自由基的伞形振动对于产物的转动激发和角分布均有较大的影响,而母体分子的转动激发只对产物的角分布有较明显的影响.     

Optical diagnostics for temperature measurement in a DC arcjet reactor used for diamond deposition

2 a-state in this plume. LIF measurements of CH are complicated by the presence of C₃ and we discuss strategies to deal with this interference. The gas temperature describing the rotational distributions obtained for NO, C₂ and CH agree within experimental error. Optical emission measurements indicate that the rotational and vibrational distributions of the excited A-state of CH and a-state of C₂ are characterized by vibrational and rotational populations which are at least 1000 K above the ground state distributions. The excited states are collisionally quenched before their population distributions equilibrate with the gas temperature. We also determine relative populations of the ground and excited states along the axis of the plume between the arcjet nozzle and the substrate and relative populations for a cross section of the jet, midway between the nozzle orifice and the substrate. The measured relative ground and excited state populations for both CH and C₂ show different trends along the plume axis, indicating that the ground and excited states of these molecules are products of different chemical mechanisms; such mechanisms are discussed. Received: 16 July 1996/Revised version: 24 September 1996     

Determining if a System is Heterogeneous: The Analysis of Single Molecule Rotational Correlation Functions and Their Limitations

Single molecule spectroscopy can be utilized to measure distributions of individual molecular properties that may be averaged out in the ensemble measurement. For example, complex dynamics in disordered systems can be investigated by observing single molecule rotations via fluorescence spectroscopy. The rotational time of a single transient can be calculated from the correlation function of the reduced linear dichroism signal which fluctuates over time as the molecule reorients in its surroundings. Distributions of rotational time constants can be used to characterize the heterogeneity of molecular environments in the material. This paper reviews some theoretical studies on (1) the high numerical aperture effects on the final correlation function, and how it can be related to optical anisotropy decays in a bulk measurement; (2) the statistical errors resulting from the finite observation length that will propagate into distributions of rotational times. These lead to the discussions on how to interpret correctly the distribution of properties measured from a set of single molecule data, and to determine if in fact the system is heterogeneous.     

Glass transitions in quasi-two-dimensional suspensions of colloidal ellipsoids

We observed a two-step glass transition in monolayers of colloidal ellipsoids by video microscopy. The glass transition in the rotational degree of freedom was at a lower density than that in the translational degree of freedom. Between the two transitions, ellipsoids formed an orientational glass. Approaching the respective glass transitions, the rotational and translational fastest-moving particles in the supercooled liquid moved cooperatively and formed clusters with power-law size distributions. The mean cluster sizes diverge in power law as they approach the glass transitions. The clusters of translational and rotational fastest-moving ellipsoids formed mainly within pseudonematic domains and around the domain boundaries, respectively.     

On the Rotational Distribution of N2 in the Ar?N2-Discharge. The O?O-Band of the Second Positive System

The rotational distribution of the O? O-band of the second positive system of N₂ was determined by the Ornstein method in the glow discharge of an argon-nitrogen mixture at medium pressure. Evidently, for the rotational R- and P-lines some straight lines can be fitted for rotational quantum numbers between 2 and 60 according to usual representation. The slopes of the curves indicate that the Boltzmann distribution does not exist for all the levels. For each of these straight lines can be declared a value of rotational temperature. The dependence of the several rotational temperatures on the discharge current is essential lower than the corresponding dependence of the gas temperature, which is calculated by means of the energy balance. The influence of the energy transfer from metastable argon atoms to ground-state nitrogen molecules on the rotational distribution seems to be insignificant. Comparisons with rotational distributions in pure nitrogen plasmas point at the influence of interactions between nitrogen species.     

Molecular dynamics simulation model of hydrogen recycling on carbon divertor for neutral transport analysis in large helical device

To perform the neutral-transport simulation with processes in which hydrogen molecules contribute to the reaction such as molecular assisted recombination, the parameters of emitted neutral particles at the wall such as the energy distributions and the form (atom or molecule) of emitted neutral particles are necessary as a boundary condition of the calculation. Therefore, in order to provide information of recycled hydrogen on the divertor to neutral-transport code, molecular dynamics simulation of a hydrogen atom injection into a carbon material is performed to obtain the distributions of emission angle and translational energy of emitted hydrogen atoms and molecules. The distributions of rotational and vibrational energies are also investigated in the case of molecular hydrogen emission. Moreover, the quantum rotational state J, and vibrational state v are estimated from the classical value obtained by the simulation.     

Calculation of torsional and rotational raman spectra of hydrogen peroxide

We present calculated intensity distributions in torsional, rotational, and torsional-rotational Raman lines in spectra of hydrogen peroxide. Ab initio calculations of polarizability tensor components as functions of internal rotation angle were carried out in the HF/6-311G approximation. It is shown that the structure and transformational properties of the polarizability tensor components of hydrogen peroxide in extended molecular symmetry group G₄(EM) permit formation of purely rotational and torsional and rotational-torsional Raman spectra. Common expressions to calculate Raman line intensities governed by torsional and rotational motions of the non-rigid symmetric top molecule are obtained. The torsional components of the line intensities have been calculated by estimating the appropriate matrix elements. The contribution of rotational components has been calculated using the 3j-symbols technique.     

Role of highest occupied molecular orbitals in molecular field-free alignment by a femtosecond pulse

This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent Schr?dinger equation. The broad rotational wave packets excited by the femtosecond pulse are defined in conjugate angle space, and their coefficients are obtained by solving a set of coupled linear equations. Both single molecule orientation angles and an ensemble of O₂ and CO molecule angular distributions are calculated in detail. The numerical results show that, for single molecule highest occupied molecular orbital (HOMO) symmetry σ tends to have a molecular orientation along the laser polarization direction and the permanent dipole moment diminishes the mean of the orientation angles; for an ensemble of molecules, angular distributions provide more complex and additional information at times where there are no revivals in the single molecule plot. In particular, at the revival peak instant, with the increase of temperature of the molecular ensemble, the anisotropic angular distributions with respect to the laser polarization direction of the π _g orbital gradually transform to the symmetrical distributions regarding the laser polarization vector and for two HOMO configurations angular distributions of all directions are confined within a smaller angle when the temperature of the molecular ensemble is higher.     

Multidimensional Langevin approach to description of near-barrier heavy-ion fusion and deep-inelastic collisions

A six-dimensional Langevin approach is developed for the analysis of near-barrier heavy-ion fusion and deep-inelastic collisions. In its framework, vibrational and rotational degrees of freedom of both nuclei are taken into account explicitly. Calculated fusion cross sections, compound nuclei spin distributions, and angular and energy distributions of deep-inelastic products show satisfactory agreement with experimental data.     

低振动激发HeI2分子振动预离解寿命和终转动态分布

用含时黄金规则波包法，对ＨｅＩ２分子在低初始振动激发（ｖ＜１２）态下振动预离解动力学作了全维量子力学计算。所预言的总衰变宽度和寿命与谱线宽和皮秒时间分解的实时态－态测量外推数据符合得相当好。计算的总衰变宽度对初始振动态ｖ是敏感的并呈现一种非线性关系。结果表明低振动激发ＨｅＩ２分子衰变模式仍应是量子力学的。除终态相互作用对决定终转动分布有重要作用以外，首次发现，低振动激发态的初始特性也能显著影响终转动态分布。用Ｉ２的转动常数对ｖ的关系合理地解释了这个独特现象     

Scattering of N2 from Ni(111)

A cold (T_rot<10 K) beam of N₂ with an initial translational energy of 0.40 eV strikes an Ni(111) surface at surface temperatures from 300 to 873 K at several incident angles from 15 to 60°. The rotational energy and angular distributions of the scattered molecules are probed using (2+1) resonance-enhanced multiphoton ionization. Molecules scattered in the specular direction have mean rotational energies that are independent of surface temperature, whereas those scattered at angles far from the specular show a dependence on surface temperature, caused likely by multiple collisions with the surface before escape. A rotational rainbow, seen in systems such as CO–Ni(111) and N₂–Ag(111), is not seen in this system. For molecules that scatter close to the specular direction, approximately 10% of the initial translational energy is converted into rotational energy of the scattered N₂. For surface temperatures above room temperature, the angular distributions indicate that molecules that scatter into low-J states also tend to exit in a broad peak (10–20° FWHM) near the specular, and this peak is broadened with increasing incident angle. The molecules that scatter into high-J states have a much broader distribution, indicating that they are trapped rotationally during the initial collision and suffer multiple collisions before leaving the surface.     

Rotational relaxation rates in CO-He mixtures

The rotational level populations of CO molecules were measured in CO(<10%) + He free jets by electron beam fluorescence (in a stationary jet) and resonantly enhanced multiphoton ionization (in a pulsed jet). The measured evolution of the non-equilibrium rotational energy was used to derive the rotational relaxation cross-sections in the temperature range from 6 K to 140 K. To compare and analyse on a common basis all available experimental data (ours and others) on rotational relaxation of CO in He, the infinite order sudden approximation was explored. The following quantities were investigated: integral rotationally inelastic cross-sections, state-to-state rate coefficients, rotational relaxation times, line broadening coefficients, and non-equilibrium rotational energy distributions in a free jet.     

全固态光子带隙光纤第1带隙内模场分布特性

利用多极法计算了全固态光子带隙光纤第1带隙内不同波长处的基模模场分布,得到2维归一化光强分布特性.由于该光纤具有三角形(C<,6v>)的对称结构,影响了光纤内的模场分布,为此计算了该结构两个具有代表性的方向上的模场分布,分析了带隙内两个不同的结构方向上的模场分布特性.结果表明.在长波长区域,两个方向上的模场半径并不相等,但都随波长的增加而减小,其变化规律与全内反射导光的光纤不同.     

Symmetry properties of fluctuations in an actively driven rotor

We investigate rotational dynamics of an actively driven rotor through experiments and numerical simulations. While probability density distributions of rotor angular velocity are strongly non-Gaussian, relative probabilities of observing rotation in opposite directions are shown to be linearly related to the angular velocity magnitude. We construct a stochastic model to describe transitions between different states from rotor angular velocity data and use the stochastic model to show that symmetry properties in probability density distributions are related to the detailed fluctuation relation(FR) of entropy productions.     

Product state distributions and rotational polarization for the crossed beam reactions of Ca with F2 and NF3

Product state distributions of the CaF products from the thermal crossed beam reactions Ca + F₂ and Ca + NF₃ have been measured using laser induced fluorescence (LIF) techniques. We obtain information about the rotational and vibrational distributions by generating synthetic band profiles and comparing them with those observed. The inverted vibrational distributions indicate direct reaction mechanisms. For Ca + F₂ the fractionf′ of energy is nearly half going into product translation and the remainder being devided nearly equally between product rotation and vibration. For Ca + NF₃ the largest fraction of the available reaction exoergicity goes into vibrational excitation of the newly formed CaF products. In addition, we have probed the rotational polarization of CaF product molecules. This gives direct information on the role of angular momentum alignment in reactive scattering.