Calculation of semiclassical free energy differences along non-equilibrium classical trajectories

We have derived several relations, which allow the evaluation of the system free energy changes in the leading order in $\hbar^{2}$ along classically generated trajectories. The results are formulated in terms of purely classical Hamiltonians and trajectories, so that semiclassical partition functions can be computed, e.g., via classical molecular dynamics simulations. The Hamiltonians, however, contain additional potential-energy terms, which are proportional to $\hbar^{2}$ and are temperature-dependent. We discussed the influence of quantum interference on the nonequilibrium work and problems with unambiguous definition of the semiclassical work operator

Molecular reorientation in hydrogen-bonding liquids: through algebraic ∼t−3/2\sim t^{-3/2} relaxation toward exponential decay

We present a model for the description of orientational relaxation in hydrogen-bonding liquids. The model contains two relaxation parameters which regulate the intensity and efficiency of dissipation, as well as the memory function which is responsible for the short-time relaxation effects. It is shown that the librational portion of the orientational relaxation is described by an algebraic $\sim t^{-3/2}$ contribution, on top of which more rapid and non-monotonous decays caused by the memory effects are superimposed. The long-time behavior of the orientational relaxation is exponential, although non-diffusional. It is governed by the rotational energy relaxation. We apply the model to interpret recent molecular dynamic simulations and polarization pump-probe experiments on $HOD$ in liquid $D_{2}O$ [C. J. Fecko et al, J. Chem. Phys. 122, 054506 (2005)]

Velocity dependence of friction and Kramers relaxation rates

We study the influence of the velocity dependence of friction on the escape of a Brownian particle from the deep potential well ($E_{b} \gg k_{B}T$, $E_{b}$ is the barrier height, $k_{B}$ is the Boltzmann constant, $T$ is the bath temperature). The bath-induced relaxation is treated within the Rayleigh model (a heavy particle of mass $M$ in the bath of light particles of mass $m\ll M$) up to the terms of the order of $O(\lambda^{4})$, $\lambda^{2}=m/M\ll1$. The term $\sim 1$ is equivalent to the Fokker-Planck dissipative operator, and the term $\sim \lambda^{2}$ is responsible for the velocity dependence of friction. As expected, the correction to the Kramers escape rate in the overdamped limit is proportional to $\lambda^{2}$ and is small. The corresponding correction in the underdamped limit is proportional to $\lambda^{2}E_{b}/(k_{B}T)$ and is not necessarily small. We thus suggest that the effects due to the velocity-dependent friction may be of considerable importance in determining the rate of escape of an under- and moderately damped Brownian particle from a deep potential well, while they are of minor importance for an overdamped particle

Microscopic origin of the jump diffusion model

The present paper is aimed at studying the microscopic origin of the jump diffusion. Starting from the $N$-body Liouville equation and making only the assumption that molecular reorientation is overdamped, we derive and solve the new (hereafter generalized diffusion) equation. This is the most general equation which governs orientational relaxation of an equilibrium molecular ensemble in the hindered rotation limit and in the long time limit. The generalized diffusion equation is an extension of the small-angle diffusion equation beyond the impact approximation. We establish the conditions under which the generalized diffusion equation can be identified with the jump diffusion equation, and also discuss the similarities and differences between the two approaches

Experimental analysis and numerical simulation of sintered micro-fluidic

This paper investigates the use of numerical simulations to describe solid state diffusion of a sintering stage during a Powder Hot Embossing (PHE) process for micro-fluidic components. Finite element analysis based on a thermo-elasto-viscoplastic model was established to describe the densification process of a PHE stainless steel porous component during sintering. The corresponding parameters such as the bulk viscosity, shearing viscosity and sintering stress are identified from dilatometer experimental data. The numerical analyses, which were performed on a 3D micro-structured component, allowed comparison between the numerical predictions and experimental results of during a sintering stage. This comparison demonstrates that the FE simulation results are in better agreement with the experimental results at high temperatures

Physical modelling of amorphous thermoplastic polymer and numerical simulation of micro hot embossing process

Micro hot embossing process is considered as one of the most promising micro replication processes for manufacturing of polymeric components, especially for the high aspect ratio components and large surface structural components. A large number of hot embossing experimental results have been published, the material modelling and processes simulation to improve the quality of micro replication by hot embossing process are still lacking. This paper consists to 3D modelling of micro hot embossing process with amorphous thermoplastic polymers, including the mechanical characterisation of polymers properties, identification of the viscoelastic behaviour law of the polymers, numerical simulation and experimental investigation of micro hot embossing process. Static compression creep tests have been carried out to investigate the selected polymers’ viscoelastic properties. The Generalized Maxwell model has been proposed to describe the relaxation modulus of the polymers and good agreement has been observed. The numerical simulation of the hot embossing process in 3D has been achieved by taking into account the viscoelastic behaviour of the polymers. The microfluidic devices with the thickness of 2 mm have been elaborated by hot embossing process. The hot embossing process has been carried out using horizontal injection/compression moulding equipment, especially developed for this study. A complete compression mould tool, equipped with the heating system, the cooling system, the ejection system and the vacuum system, has been designed and elaborated in our research. Polymer-based microfluidic devices have been successfully replicated by the hot embossing process using the compression system developed. Proper agreement between the numerical simulation and the experimental elaboration has been observed. It shows strong possibility for the development of the 3D numerical model to optimize the micro hot embossing process in the future

Students of Haitian Descent in American Schools: Challenges and Issues

This paper examines the ways the reception of students of Haitian descent in this country has shaped their educational careers. Additionally, this paper explores the racial, cultural, and individual differences that need to be understood in order to help educators, parents, and students make their schooling a positive experience

Self-similarity of single-channel transmission for electron transport in nanowires

We demonstrate that the single-channel transmission in the resonance tunneling regime exhibits self-similarity as a function of the nanowire length and the energy of incident electrons. The self-similarity is used to design the nonlinear transformation of the nanowire length and energy which, on the basis of known values of transmission for a certain region on the energy-length plane, yields transmissions for other regions on this plane. Test calculations with a one-dimensional tight-binding model illustrate the described transformations. Density function theory based transport calculations of Na atomic wires confirm the existence of the self-similarity in the transmission