Sonoluminescence intensity and ultrasonic cavitation temperature in organic solvents: Effects of generated radicals

Ultrasonic cavitation in organic solvents remains poorly understood in contrast with aqueous systems, largely because of complexities related to solvent decomposition. In this study, we sonicated different types of organic solvents (i.e. linear alkanes, aliphatic alcohols, aromatic alcohols, and acetate esters) under argon saturation. The average temperature of the cavitation bubbles was estimated using the methyl radical recombination method. We also discuss the effects of the physical properties of the solvents, such as vapor pressure and viscosity, on the cavitation temperature. The average cavitation bubble temperature and sonoluminescence intensity were higher in organic solvents with lower vapor pressure; for aromatic alcohols, these values were particularly high. It was found that the specific high sonoluminescence intensities and average cavitation temperatures exhibited in aromatic alcohols are caused by the highly resonance-stable generated radicals. The results obtained in this study are very useful for acceleration of sonochemical reaction in organic solvents, which are indispensable for organic synthesis and material synthesis.     

On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge‐Transfer Complexation

It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge‐transfer (CT) complexation reaction. By studying the trimethylated‐benzene–I₂ CT complex, we find that VSC induces large changes in the equilibrium constant K_DA of the CT complex, reflecting modifications in the ΔG° value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, ΔG° either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences.     

Combining Complex and Radial Slave Boson Fields within the Kotliar–Ruckenstein Representation of Correlated Impurities

The gauge symmetry group of any slave boson representation allows to gauge away the phase of bosonic fields. One benefit of this radial field formulation is the elimination of spurious Bose condensations when saddle-point approximation is performed. Within the Kotliar–Ruckenstein representation, three of the four bosonic fields can be radial while the last one has to remain complex. In this work, the procedure to carry out the functional integration involving constrained fermionic fields, complex bosonic fields, and radial bosonic fields is presented. The correctness of the representation is verified by exactly evaluating the partition function and the Green's function of the Hubbard model in the atomic limit.     

The changes in free energies and entropies from analytical radial distribution functions

The changes in Helmholtz free energies and entropies in dense fluids have been evaluated using three known analytical expressions for radial distribution functions (RDFs) of Lennard–Jones (L-J) fluid. This method provides a simpler and a more expeditious way for the calculation of free energy and entropy in L-J dense fluids through statistical mechanics. Previously, integral equations or perturbation theories were used for this purpose. Such approach not only tests the power of analytical distribution functions in predicting the changes in Helmholtz free energies and entropies, but also specifies better expressions in determining these properties. The results are compared with experimental data and an accurate analytic equation of state for the L-J fluid. It is shown if an expression properly presents RDFs as a function of interparticle distance, density and temperature, it is possible to calculate the changes in Helmholtz free energies and entropies from analytical distribution functions.     

中性线修正型变截面梁类构件压电控制

传统绝对节点坐标法(absolute nodal coordinate formulation,ANCF)在变截面梁类构件建模过程中常以几何中位线等效构造单元中性线,难以对变截面单元位移场状态进行精确描述.为解决此类问题,本文以中细型变截面梁类构件为研究对象,深入考虑变截面结构几何因素及复合材料属性对变截面梁类构件中性...     

Lp径向Blaschke-Minkowski同态的Lp对偶几何表面积

2006年,Schuster提出了径向Blaschke-Minkowski同态的概念.随后,汪卫等人将其推广到L_p径向Blaschke-Minkowski同态.本文结合L_p对偶几何表面积,建立了L_p径向Blaschke-Minkowski同态的若干不等式,包括Brunn-Minkowski型不等式和单调不等式.并给出了L_p径向Blaschke-Minkowski同态的Busemann-Petty问题的肯定和否定形式.     

The absence of physical-aging effects on the surface relaxations of rubbed polystyrene

Extensive experimental results are presented to reveal the relaxations of polystyrene surface deformed by rubbing with a velvet cloth. We found that surface topographic features, such as ditches and ridges created by rubbing, relax at temperatures at about 20^° C below the bulk glass transition temperature of the polystyrene for a molecular weight of 442 kg/mol, even though we estimate the Laplace Pressure driving the relaxation to be 1/500 of the yield limit. The relaxation is independent of the thermal history before the rubbing process, and post rubbing thermal history below 55^° C . In other words, physical-aging processes at 23^° C for up to 7 days and at 50^° C for 2 days, which would have drastic effects on the relaxations of bulk polymers, have little effects on the relaxations of rubbed surfaces. This is consistent with the mobility enhancement in the surface layer previously reported in the literature.     

Influence of radiation damage on lattice vibration parameters in crystalline and vitreous SiO2

The influence of radiation damage on a number of lattice vibration parameters in two SiO₂ modifications was investigated using IR reflectance spectroscopy. The radiation kinetics of changes in spectral characteristics of SiO₂ fundamental vibrations in crystalline and glassy states were determined. The reflectivity coefficient and the frequency of degenerate vibrations as functions of dose showed minima, the locations of which were governed by the type of sample. At high neutron irradiation doses (10²¹ cm⁻²), certain characteristics of the bands had the same values for both modified materials. Features of the radiation kinetics of sample dynamic parameters were determined. It was deduced that the specific character of the observed radiation-induced changes in spectral and dynamic parameters of vibrations near degenerate modes was due to both the accumulation of radiation damage and a change in the force field surrounding bridging bonds, which is related to a change in the SiO₂ structure. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 354–358, May–June, 2008.     

Fast evaluation of polyharmonic splines in three dimensions

M. J. D. Powell ^{This paper concerns the fast evaluation of radial basis functions.It describes the mathematics of hierarchical and fast multipolemethods for fast evaluation of splines of the form where is a positive integer andp is a low-degree polynomial. Splines s of this form are polyharmonicsplines in 3 and have been found to be very useful for providingsolutions to scattered data interpolation problems in 3. Asit is now well known, hierarchical methods reduce the incrementalcost of a single extra evaluation from O(N) to O(log N) operationsand reduce the cost of a matrix–vector product (evaluationof s at all the centres) from O(N2) to O(N log N) operations.We give appropriate far- and near-field expansions, togetherwith error estimates, uniqueness theorems and translation formulae.A hierarchical code based on these formulae is detailed andsome numerical results are given.}     

M-RNA碱基复合物(M=Ca+和Mg+)特征振动的密度泛函理论分析

采用密度函数理论的B3LYP交换关联能泛函在6-311+G(2df,2p)基组水平上,优化计算了Ca+,Mg+与RNA碱基嘧啶各同分异构体形成稳定复合物的结构,发现其中C1M,T1M和U1M(M=Ca+和Mg+)为最稳定复合物,并对这些复合物红外振动进行了计算.计算结果显示碱基嘧啶单体主要存在的两个红外特征振动,是由环振动和环外氧原子及与其成键的环上碳原子之间产生伸缩振动引起的.当形成复合物时,由于离子的参与,使单体碱基分子的振动情况发生了改变,主要表现在离子倾向于与环外负电子原子N和O原子成键,使与离子直接作用环外原子参与的特征振动频率减小,谱线红移;不与离子直接作用环外原子引起的特征振动频率增大,谱线蓝移.