Derivation of a temperature-dependent accommodation coefficient for use in modeling laser-induced incandescence of soot

This paper presents a derivation of an expression to estimate the accommodation coefficient for gas collisions with a graphite surface, which is meant for use in models of laser-induced incandescence (LII) of soot. Energy transfer between gas molecules and solid surfaces has been studied extensively, and a considerable amount is known about the physical mechanisms important in thermal accommodation. Values of accommodation coefficients currently used in LII models are temperature independent and are based on a small subset of information available in the literature. The expression derived in this study is based on published data from state-to-state gas-surface scattering experiments. The present study compiles data on the temperature dependence of translational, rotational, and vibrational energy transfer for diatomic molecules (predominantly NO) colliding with graphite surfaces. The data were used to infer partial accommodation coefficients for translational, rotational, and vibrational degrees of freedom, which were consolidated to derive an overall accommodation coefficient that accounts for accommodation of all degrees of freedom of the scattered gas distributions. This accommodation coefficient can be used to calculate conductive cooling rates following laser heating of soot particles.     

Measurement of rotational temperature in CO2 waveguide laser medium

A small-signal gain in CO₂ waveguide laser medium has been measured on rotational-vibrational transitions in the P-branch of the (0, 0, 1)-(0, 2⁰, 0) band. It has been found that the rotational temperature is well defined in the waveguide laser system where high excitation power is injected and a large amount of energy is flowing through vibrational, rotational, and translational degrees of freedom. The rotational temperature is slightly higher than the translational temperature.     

含振动能激发Boltzmann模型方程气体动理论统一算法验证与分析

为模拟研究高温高马赫数下多原子气体内能激发对跨流域非平衡流动的影响,将转动能、振动能分别作为气体分子速度分布函数的自变量,把转动能和振动能处理为连续分布的能量模式,将Boltzmann方程的碰撞项分解成弹性碰撞项和非弹性碰撞项,同时将非弹性碰撞按一定松弛速率分解为平动-转动能松弛过程和平动-转动-振动能松弛过程,构造了一类考虑振动能激发的Boltzmann模型方程,并证明了其守恒性和H定理.基于内部能量变量对分布函数无穷积分,引入三个约化速度分布函数,得到一组考虑振动能激发的约化速度分布函数控制方程组,使用离散速度坐标法,基于LU-SGS隐式格式和有限体积法求解离散速度分布函数,建立含振动能激发的气体动理论统一算法.通过开展高稀薄流到连续流圆柱绕流问题统一算法与直接模拟蒙特卡罗法模拟结果对比分析,特别是过渡流区平动、转动、振动非平衡效应对绕流流场与物面力热特性的影响机制,证实了所建立的含振动能激发的Boltzmann模型方程及气体动理论统一算法的准确可靠性.     

密度泛函理论研究LiX(X=H,D,T)体系的热力学性质

运用量子力学从头计算方法,计算了氢化锂(氘化锂、氚化锂)分子的部分热力学函数和力学、光谱学性质。基于准简谐Debye模型,计算了固体Li的振动内能、振动和电子熵,探讨了Li吸收氢同位素气体生成一氢化物的反应熵变、生成焓变和生成Gibbs自由能及氢同位素的平衡离解压。结果显示:在Li吸收同位素气体生成一氢化物的反应中,生成焓变和反应熵变均为负值,且随温度升高,绝对值越大,Gibbs自由能则向正的方向增加。热力学上,在相同温度和压力下,氢置换一氢化物中的氘和氚、及氘置换氚的反应更易发生。     

First-principles calculations of precursor adsorption on substrate during atomic layer deposition: The example of SiO2 deposition using tris(dimethylamino)silane

In this study, we investigate the reaction mechanisms of precursor adsorption during the atomic layer deposition (ALD) using density functional theory (DFT) calculations and ideal-gas methods; herein, we considered adsorption of tris(dimethylamino)silane (TDMAS) on a hydroxylated SiO₂ surface to be the example for our investigation. When the reaction free energy is calculated, the DFT results obtained at 0 K suggest that the dissociation of a hydrogen atom from TDMAS is favorable upon TDMAS adsorption, which is inconsistent with the experimental results where one dimethylamino group is released. The experimental results can be accurately predicted when enthalpy and entropy changes are considered at elevated temperatures, thereby indicating the significance of finite-temperature effects in free-energy changes for solid-gas reactions. We analyze the changes in enthalpy and entropy and find that dimethylamine is a more favorable gaseous product than H₂ owing to its larger translational and rotational entropy.     

Back flux at polyatomic gas expansion for pulsed laser evaporation

The back flux value at polyatomic gas expansion under pulsed laser evaporation is determined on the basis of one-dimensional direct Monte Carlo simulation. Calculations are performed for a wide range of evaporated matter amount. Taking into account rotational and vibrational degrees of freedom substantially increases the back flux. Dependence of the back recondensed fraction on the relaxation collision number is shown. The data are generally in good agreement with available analytical predictions. Importance of consideration of energy transfer from the internal degrees of freedom to the translational ones is illustrated by an example of pulsed laser evaporation of polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA).     

Partitioning Entropy with Action Mechanics: Predicting Chemical Reaction Rates and Gaseous Equilibria of Reactions of Hydrogen from Molecular Properties

Our intention is to provide easy methods for estimating entropy and chemical potentials for gas phase reactions. Clausius’ virial theorem set a basis for relating kinetic energy in a body of independent material particles to its potential energy, pointing to their complementary role with respect to the second law of maximum entropy. Based on this partitioning of thermal energy as sensible heat and also as a latent heat or field potential energy, in action mechanics we express the entropy of ideal gases as a capacity factor for enthalpy plus the configurational work to sustain the relative translational, rotational, and vibrational action. This yields algorithms for estimating chemical reaction rates and positions of equilibrium. All properties of state including entropy, work potential as Helmholtz and Gibbs energies, and activated transition state reaction rates can be estimated, using easily accessible molecular properties, such as atomic weights, bond lengths, moments of inertia, and vibrational frequencies. We conclude that the large molecular size of many enzymes may catalyze reaction rates because of their large radial inertia as colloidal particles, maximising action states by impulsive collisions. Understanding how Clausius’ virial theorem justifies partitioning between thermal and statistical properties of entropy, yielding a more complete view of the second law’s evolutionary nature and the principle of maximum entropy. The ease of performing these operations is illustrated with three important chemical gas phase reactions: the reversible dissociation of hydrogen molecules, lysis of water to hydrogen and oxygen, and the reversible formation of ammonia from nitrogen and hydrogen. Employing the ergal also introduced by Clausius to define the reversible internal work overcoming molecular interactions plus the configurational work of change in Gibbs energy, often neglected; this may provide a practical guide for managing industrial processes and risk in climate change at the global scale. The concepts developed should also have value as novel methods for the instruction of senior students.     

Rotational statistics and thermodynamic functions of hydrogen peroxide

Partition functions for both the rotational modes (hindered internal rotation and overall rotation) of the hydrogen peroxide (H₂O₂) molecule in the ground electronic state are studied using quantum and classical Gibbsian statistical mechanics. The partition functions are used to calculate rotational thermodynamic functions (internal energy, enthalpy, Helmholtz free energy, Gibbs free energy and entropy) of a hydrogen peroxide gas of weakly interacting molecules at temperatures above 300 K.     

Semiclassical theory of vibrational,rotational and translational energy exchange in collisions of polyatomic molecules

We derive a theory of inter- and intramolecular transfer of vibrational, rotational and translational energy in collisions of polyatomic molecules, in the case that only short range forces are important. Normal mode vibrations of molecules are treated quantum mechanically whereas translations and rotations are assumed to be classical degrees of freedom. We are able to show that, in case of short range forces, the energy exchange in binary collisions is essentially governed by an effective mass which is given by an algebraic function of the usual reduced mass and moments of inertia and depends also on the relative orientation of the two molecules. As an application of the theory, we calculated the probabilities for collision-induced 1 →0 transitions of the v ₃ mode in pure CH₃I, CH₃Br and CH₃Cl gases. The calculated values are close to the experimental vibrational deactivation probabilities.     

Cavity cooling of internal molecular motion

We predict that it is possible to cool rotational, vibrational, and translational degrees of freedom of molecules by coupling a molecular dipole transition to an optical cavity. The dynamics is numerically simulated for a realistic set of experimental parameters using OH molecules. The results show that the translational motion is cooled to a few muK and the internal state is prepared in one of the two ground states of the two decoupled rotational ladders in a few seconds. Shorter cooling times are expected for molecules with larger polarizability.     

Schwingungsrelaxation von CO2 in Gemischen mit Helium

The excitation mechanisms of the vibrational degrees of freedom of CO₂ in gaseous mixtures with 0–99 per cent helium have been studied by acoustic absorption measurements. It turns out that the excitation always occurs in binary collisions, in which helium as collision partner is 22 times more efficient than CO₂ itself. A monotonic increase of the relaxing part of the specific heat with increasing helium content, in excess of the total vibrational specific heat of the mixture, can be explained as influence of simultaneous rotational-vibrational transitions. Hereby those transitions, in which the vibrational and rotational energy of a CO₂ molecule changes oppositely, are more frequent than those with like energy changes.     

Entropy Effects in Intermolecular Associations of Crown-Ethers and Cyclodextrins with Amino Acids in Aqueous and in Non-Aqueous Media

The analysis of the ratios of entropy and enthalpy characteristics and their contributions to the change in the Gibbs energy of intermolecular interactions of crown ethers and cyclodextrins with amino acids is carried out. Two different types of macrocycles were chosen for examination: crown ethers with a hydrophilic interior and cyclodextrins with a hydrophobic inner cavity and a hydrophilic exterior. The thermodynamics of complex formation of crown ethers and cyclodextrins with amino acids in water and aqueous-organic solvents of variable composition was examined. The contributions of the entropy solvation of complexes of 18-crown-6 with glycine, alanine, phenylalanine to the change in the entropy of complexation in water-ethanol and water-dimethyl sulfoxide solvents was calculated and analyzed. It was found that the ratios of the entropy and enthalpy solvation of the reagents for these systems have similar trends when moving from water to aqueous-organic mixtures. The relationship between the thermodynamic characteristics and structural features of the complexation processes between cyclodextrins and amino acids has been established. The thermodynamic enthalpy–entropy compensation effect was revealed, and its features for complexation of cyclodextrins and 18-crown-6 were considered. It was concluded that, based on the thermodynamic parameters of molecular complexation, one could judge the mode of the formation of complexes, the main driving forces of the interactions, and the degree of desolvation.     

GaP及GaAs中Fe深受主中心的反键态及有关性质

本文通过计算得到GaP及GaA₃中Fe能级基态空穴跃迁时引起的晶格振动熵变,证明Fe受主形成反键中心,得到空穴—→价带跃迁时的焓变与自由能变的温度关系,并与实验结果作了比较,说明Fe中心空穴热离化能比光离化能高是合理的。 关键词：     

Time-resolved spectroscopy in study of the intramolecular vibrational dynamics: Recent results and future prospects

Applications of spectroscopic methods in real-time investigations of the vibrational energy redistribution in an isolated polyatomic molecule are reviewed. The results of the latest experiments with propyne and its derivatives according to the pump-probe scheme with the use of Raman spectroscopy are reported. The main result is the key role of the energy transfer between the vibrational and rotational degrees of freedom in the molecules studied.     

Defects in silicon: the role of vibrational entropy

Vibrational free energies are calculated from first-principles in the same Si periodic supercells routinely used to perform defect calculations. The specific heat, vibrational entropy, and zero-point energy obtained in defect-free cells are very close to the measured values. The importance of the vibrational part of the free energy is studied in the case of two defect problems: the relative energies of the H₂ and H₂^∗ dimers and the binding energy of a copper pair. In both cases, the vibrational entropy term causes total energy differences to change by about 0.2 eV between 0 and 800 K. We also comment on the rotational entropy in the case of H₂ and the configurational entropy in the case of the Cu pair. These examples illustrate the importance of extending first-principles calculations of defects in semiconductors to include free energy contributions.     

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.     

Vibrational autoionization in rydberg states of ammonia

Rotationally resolved photoelectron spectroscopy is used to elucidate the mechanism for vibrational autoionization via the nontotally symmetric umbrella vibration of ammonia ( NH3). This mechanism depends strongly on the character of the autoionizing level, and the data demonstrate that both the electronic and rotational degrees of freedom can compensate for the change in vibrational symmetry that occurs for odd changes in the quantum number of the umbrella vibration. This result has implications for models of the mode dependence of vibrational autoionization in polyatomic molecules.     

振动和转动激发对N2在Fe(111)表面解离吸附的影响

N₂的解离化学吸附是工业合成氨的速控步骤. 基于最近构建的六维势能面,本文研究了N₂的初始振动激发和转动激发在Fe(111)表面的反应性的作用. 由于该反应具有重要的量子效应,通过六维量子动力学计算研究了入射能量低于1.6 eV 时振动激发的效应. 并采用准经典轨线计算揭示了高入射能量下的振动和转动激发的影响. 通过这些研究发现增加平动能量在一定程度上能提高解离几率,振动激发或转动激发能更有效地促进解离. 这项研究为重原子分子-表面反应的模式特异性动力学提供了有价值的见解.