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

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

Directed motion and useful work from an isotropic nonequilibrium distribution

We demonstrate that a gas of classical particles trapped in an external asymmetric potential undergoes a quasiperiodic motion, if the temperature of its initial velocity distribution $T_{ne}$ differs from the equilibrium temperature, $T_{eq}$. The magnitude of the effect is determined by the value of $T_{ne}-T_{eq}$, and the direction of the motion is determined by the sign of this expression. The "loading'' and "unloading'' of the gas particles change directions of their motion, thereby creating a possibility of shuttle-like motion. The system works as a Carnot engine where the heat flow between kinetic and potential parts of the nonequilibrium distribution produces the useful work

Calculations of canonical averages from the grand canonical ensemble

Grand canonical and canonical ensembles become equivalent in the thermodynamic limit, but when the system size is finite the results obtained in the two ensembles deviate from each other. In many important cases, the canonical ensemble provides an appropriate physical description but it is often much easier to perform the calculations in the corresponding grand canonical ensemble. We present a method to compute averages in canonical ensemble based on calculations of the expectation values in grand canonical ensemble. The number of particles, which is fixed in the canonical ensemble, is not necessarily the same as the average number of particles in the grand canonical ensemble