Hydrogen bond lifetimes in supercritical methanol–water mixtures via MD simulation

Dynamical features of hydrogen bonds in methanol–water mixtures have been analysed in terms of lifetime in the wide range of conditions, including supercritical states, using a molecular dynamics simulation with flexible potential models. Hydrogen bond characteristics in methanol–water mixtures were investigated by considering the combination of molecular species and donor–acceptor of hydrogen-bonded molecules. The hydrogen bond lifetimes mainly depend on temperature, and those in supercritical condition were about 1/10th of that at ambient condition. Focusing on the composition dependence of the hydrogen bond lifetime, the unique behaviour of that resulting from hydration structure was observed. Moreover, the molecular combination, which showed the largest hydrogen bond lifetime, was different for ambient and high temperature and high pressure conditions. The relationship between hydrogen bond lifetime and molar volume was also calculated to discuss the hydrogen bond lifetime in terms of the collision frequency of molecules and the intermolecular distance.     

Methods for calculating the desorption rate of an isolated molecule from a surface: Water on MgO(0 0 1)

We present two types of Molecular Dynamics (MD) simulation for calculating the desorption rate of molecules from a surface. In the first, the molecules move freely between two surfaces, and the desorption rate is obtained either by counting the number of desorption events in a given time, or by looking at the average density of the molecules as a function of distance from the surface and then applying transition state theory (TST). In the second, the potential of mean force (PMF) for a molecule is determined as a function of distance from the surface and the desorption rate is obtained by means of TST. The methods are applied to water on the MgO(0 0 1) surface at low coverage. Classical potentials are used so that long simulations can be performed, to minimise statistical errors. The two sets of MD simulations agree well at high temperatures. The PMF method reproduces the 0 K adsorption energy of the molecule to within 5 meV, and finds that the well depth of the PMF is not linear with temperature. This implies the prefactor frequency f in the Polanyi-Wigner equation is a function of temperature, increasing at lower temperatures due to the reduction of the available configuration space associated with an adsorbed molecule compared with a free molecule.     

A predissociative triplet Rydberg state of the nitrogen molecule studied by near-infrared diode laser kinetic spectroscopy

A new ³Π-³Σ band was observed in a discharge plasma of the nitrogen molecule and helium using near-infrared diode laser kinetic spectroscopy. All the lines in this band exhibited line broadening of more than 0.1 cm⁻¹. Rotational analysis revealed that the lower state of the transition was the state of N₂, which had already been studied in the D³Σ-E³Σ band. The term value and rotational constant suggested that the upper state is the G³Π_u Rydberg state with an electron configuration of (N₂⁺:X²Σ core)(3pπ_u). The line broadening is attributed to predissociation through a homogeneous interaction with a repulsive Π_u state.     

Surface reconstructions of InGaAs alloys

The surface reconstructions of In_xGa_1−xAs alloys grown by molecular beam epitaxy on the (0 0 1) surfaces of GaAs and InAs have been studied by reflection high-energy electron diffraction and scanning tunnelling microscopy. A surface phase diagram is presented for the nominally strain-free alloy as a function of substrate temperature and alloy composition, and structural models for the commonly observed 3× reconstructions are discussed. Two new, electronically stable structural models are described that account for the transition of the In_xGa_1−xAs surface alloy from a c(4 × 4) to an asymmetric 3× reconstruction and that are fully consistent with all current experimental evidence.     

Effect of surface hydrogenation on the topological properties of multilayer graphene

We have investigated effects of surface hydrogenation on the topological properties of multilayer graphene by using density functional theory calculations and a tight-binding model. Hydrogen adsorption on a dimer site of a surface layer decouples the surface layer from the rest of the layers. Hydrogen adsorption on a nondimer site introduces a band mixing between the hydrogenated graphene and the rest of the graphene layers. The valley Hall effects and spin-valley-resolved Chern numbers of multilayer graphene, calculated as a function of the sublattice potential and the potential perpendicular to the layers, was found to be sensitive to details of inversion symmetry-breaking potentials. While the topological invariant depends on the adsorption site and spin polarization, surface-hydrogenated M-layer graphene was found to be topologically equivalent to (M-1)-layer graphene under inversion symmetry-breaking potentials regardless of the adsorption site.     

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采用直流驱动等离子体激励器并通过气流场的碘线表征法研究了边界表面放电等离子体对低气压超音速氦气流场的作用。实验结果表明,边界表面放电等离子体的阴极区对以超音速流动的氦气的控制作用在符合实际工程条件的低气压下是有效果的;等离子体激励器的驱动电压越高,气流场的流动控制效果越好;定性观察表明激励器的阴极板的面积越大,实际作用区域越大,相应的实际控制效果越好。     

城市景观河道中藻华暴发对水体中DOM特征的影响

城市景观河道由于接纳了不同来源的废水造成水体富营养化,因此在夏季经常暴发藻华。藻华暴发改变了水体中DOM的性状,进而影响到水体中污染物的迁移转化行为。本研究以天津市海河干流为例,采集藻华暴发前后水体样品,研究城市景观河道中藻华暴发对水体中DOM的影响。结果表明：藻华暴发后,水体中DOM的含量从26.47 mg·L-1增加到38.20 mg·L-1,水体中的TN,NH+₄-N和TON的含量也分别为暴发前的3.1倍、2.5倍和4.2倍,但是TP和NO-₃-N的含量保持稳定。C/N比值从18.51降低到6.39,而N/P比值则从5.69增加到20.10。藻华暴发使得DOM的来源从以陆源为主转变为以内源为主,水体也表现出一个逐步向磷限制转变的过程。三维荧光图谱结果显示藻华暴发后,DOM的成分从较为复杂的多种来源的有机质转变为藻类为主的有机质,而紫外特征光谱结果表明藻华暴发后DOM分子结构也从简单转变为复杂,但是水体中的腐殖质物质的含量有所下降,而类蛋白物质的含量出现了上升。利用超滤装置研究藻华暴发前后水体中不同分子量的DOM特征后发现,藻华暴发前后水体中DOM都主要以小分子的DOM为主,分子量小于10 kD的DOM占到了总的DOM的80%以上,随着分子量的增大,三维荧光特征峰强度都出现了升高趋势,而紫外特征吸收光谱也表明大分子量的DOM中可能含有更多的芳香族化合物。研究结果表明,在研究城市景观河道水体富营养化过程中要注意DOM在其中的作用,尤其是当外源污染物得到控制时,要充分考虑DOM降解对富营养化的贡献。     

Excess molar heat capacity of isobutyric acid–water binary liquid mixtures near and far away from the critical temperature

The heat capacity of the liquid–liquid mixture isobutyric acid–water has been measured for the first time near and far away from its critical point using an adiabatic calorimeter. The measurements were performed at atmospheric pressure, in the one phase region as a function of three temperatures: (1) T − T_C = 0.055 °C, (2) T − T_C = 3.055 °C, (3) T − T_C = 8.055 °C and of the composition X in acid (IA). The heat capacity C_p decreases rapidly when X increases at the used temperatures. Near the critical composition, C_p is not affected by the correlation of the concentration fluctuations.

The molar excess heat capacity of the system under investigation was analysed along the phase diagram and considered as a structural transformation effect.     

Topological monodromy as an obstruction to Hamiltonization of nonholonomic systems: Pro or contra?

The phenomenon of a topological monodromy in integrable Hamiltonian and nonholonomic systems is discussed. An efficient method for computing and visualizing the monodromy is developed. The comparative analysis of the topological monodromy is given for the rolling ellipsoid of revolution problem in two cases, namely, on a smooth and on a rough plane. The first of these systems is Hamiltonian, the second is nonholonomic. We show that, from the viewpoint of monodromy, there is no difference between the two systems, and thus disprove the conjecture by Cushman and Duistermaat stating that the topological monodromy gives a topological obstruction for Hamiltonization of the rolling ellipsoid of revolution on a rough plane.