Scaling Behavior Of Atomic Trajectories In Confined Fluids

We study the dependence of D, a quantity that has previously been associated with the fractal dimension of an atomic trajectory, on the scale on which it is measured. Single-particle and relative trajectories are generated by molecular-dynamics simulations of Lennard-Jones atoms permanently trapped in a spherical pore. Transient trapping is studied with a generalized Langevin model of dynamics. Confinement of trajectories allows D to exceed 2; in the case of permanent trapping, D diverges

Path Integral Monte Carlo Simulations Of Positronium Annihilation: From Micropores To Mesopores

Path integral Monte Carlo (PIMC) can reproduce the results of simple analytical calculations in which a single quantum particle is used to represent positronium within an idealized spherical pore. Our calculations improve on this approach by explicitly treating the positronium as a two-particle e(-), e(+) system interacting via the Coulomb interaction. We study the lifetime and the internal contact density, kappa, which controls the self-annihilation behavior for positronium in model spherical pores as a function of temperature and pore size. We compare the results with both PIMC and analytical calculations for a single-particle model

A Two-Chain Path Integral Model Of Positronium

We have used a path integral Monte Carlo technique to simulate positronium (Ps) in a cavity. The primitive propagator is used, with a pair of interacting chains representing the positron and electron. We calculate the energy and radial distribution function for Ps enclosed in a hard, spherical cavity, and the polarizability of the model Ps in the presence of an electrostatic field. We find that the positron distribution near the hard wall differs significantly from that for a single particle in a hard cavity. This leads to systematic deviations from predictions of free-volume models which treat Ps as an effective, single particle. A virial-type estimator is used to calculate the kinetic energy of the particle in the presence of hard walls. This estimator is found to be superior to a kinetic-type estimator given the interaction potentials, cavity sizes, and chain lengths considered in the current study. (C) 2000 American Institute of Physics. [S0021-9606(00)50447-4]

Computational Study Of Molecular Hydrogen In Zeolite Na-A. II. Density Of Rotational States And Inelastic Neutron Scattering Spectra

Part I of this series [J. Chem. Phys. 111, 7599 (1999)] describes a simulation of H(2) adsorbed within zeolite Na-A in which a block Lanczos procedure is used to generate the first several (9) rotational eigenstates of H(2), modeled as a rigid rotor, and equilibrated at a given temperature via Monte Carlo sampling. Here, we show that rotational states are strongly perturbed by the electrostatic fields in the solid. Wave functions and densities of rotational energy states are presented. Simulated neutron spectra are compared with inelastic neutron scattering data. Comparisons are made with IR spectra in which rotational levels may appear due to rovibrational coupling. (C) 2001 American Institute of Physics

Computational Study Of Molecular Hydrogen In Zeolite Na-A. I. Potential Energy Surfaces And Thermodynamic Separation Factors For Ortho And Para Hydrogen

We simulate H-2 adsorbed within zeolite Na-A. We use a block Lanczos procedure to generate the first several (9) rotational eigenstates of the molecule, which is modeled as a rigid, quantum rotor with an anisotropic polarizability and quadrupole moment. The rotor interacts with Na cations and O anions; interaction parameters are chosen semiempirically and the truncation of electrostatic fields is handled with a switching function. A Monte Carlo proceedure is used to sample a set of states based on the canonical distribution. Potential energy surfaces, favorable adsorbtion sites, and distributions of barriers to rotation are analyzed. Separation factors for ortho-parahydrogen are calculated; at low temperatures, these are controlled by the ease of rotational tunneling through barriers. (C) 1999 American Institute of Physics