Crystal lattice properties fully determine short-range interaction parameters for alkali and halide ions

Accurate models of alkali and halide ions in aqueous solution are necessary for computer simulations of a broad variety of systems. Previous efforts to develop ion force fields have generally focused on reproducing experimental measurements of aqueous solution properties such as hydration free energies and ion-water distribution functions. This dependency limits transferability of the resulting parameters because of the variety and known limitations of water models. We present a solvent-independent approach to calibrating ion parameters based exclusively on crystal lattice properties. Our procedure relies on minimization of lattice sums to calculate lattice energies and interionic distances instead of equilibrium ensemble simulations of dense fluids. The gain in computational efficiency enables simultaneous optimization of all parameters for Li+, Na+, K+, Rb+, Cs+, F-, Cl-, Br-, and I- subject to constraints that enforce consistency with periodic table trends. We demonstrate the method by presenting lattice-derived parameters for the primitive model and the Lennard-Jones model with Lorentz-Berthelot mixing rules. The resulting parameters successfully reproduce the lattice properties used to derive them and are free from the influence of any water model. To assess the transferability of the Lennard-Jones parameters to aqueous systems, we used them to estimate hydration free energies and found that the results were in quantitative agreement with experimentally measured values. These lattice-derived parameters are applicable in simulations where coupling of ion parameters to a particular solvent model is undesirable. The simplicity and low computational demands of the calibration procedure make it suitable for parametrization of crystallizable ions in a variety of force fields.Comment: 9 pages, 5 table

Enhanced ionization in small rare gas clusters

A detailed theoretical investigation of rare gas atom clusters under intense short laser pulses reveals that the mechanism of energy absorption is akin to {\it enhanced ionization} first discovered for diatomic molecules. The phenomenon is robust under changes of the atomic element (neon, argon, krypton, xenon), the number of atoms in the cluster (16 to 30 atoms have been studied) and the fluency of the laser pulse. In contrast to molecules it does not dissappear for circular polarization. We develop an analytical model relating the pulse length for maximum ionization to characteristic parameters of the cluster

Molecular dynamics study of solvation effects on acid dissociation in aprotic media

Acid ionization in aprotic media is studied using Molecular Dynamics techniques. In particular, models for HCl ionization in acetonitrile and dimethylsulfoxide are investigated. The proton is treated quantum mechanically using Feynman path integral methods and the remaining molecules are treated classically. Quantum effects are shown to be essential for the proper treatment of the ionization. The potential of mean force is computed as a function of the ion pair separation and the local solvent structure is examined. The computed dissociation constants in both solvents differ by several orders of magnitude which are in reasonable agreement with experimental results. Solvent separated ion pairs are found to exist in dimethylsulfoxide but not in acetonitrile. Dissociation mechanisms in small clusters are also investigated. Solvent separated ion pairs persist even in aggregates composed of rather few molecules, for instance, as few as thirty molecules. For smaller clusters or for large ion pair separations cluster finite-size effects come into play in a significant fashion.Comment: Plain LaTeX. To appear in JCP(March 15). Mpeg simulations available at http://www.chem.utoronto.ca/staff/REK/Videos/clusters/clusters.htm

SELF TRAPPED HOLE IN ALKALINE-EARTH FLUORIDES .1. STATIC PROPERTIES

Optical and spin resonance properties have been calculated for the self trapped hole (Vk centre) in CaF2, SrF2 and BaF2. The electronic properties are regarded as those of an F2- molecular ion whose internuclear spacing has been changed by the crystalline environment, and evidence is given that this is a good approximation. The spacing is obtained from a detailed lattice relaxation calculation allowing motion of many neighbours to the defect. The results are not sensitive to the different interatomic potentials used. Good agreement with experiment is obtained for optical transition energies and linewidths and for spin resonance parameters

Crystallographic Distinction between “Contact” and “Separated” Ion Pairs: Structural Effects on Electronic/ESR Spectra of Alkali-Metal Nitrobenzenides

The classic nitrobenzene anion-radical (NB-• or nitrobenzenide) is isolated for the first time as pure crystalline alkali-metal salts. The deliberate use of the supporting ligands 18-crown-6 and [2.2.2]cryptand allows the selective formation of contact ion pairs designated as (crown)M+NB-•, where M+ = K+, Rb+, and Cs+, as well as the separated ion pair K(cryptand)+NB-•both series of which are structurally characterized by precise low-temperature X-ray crystallography, ESR analysis, and UV−vis spectroscopy. The unusually delocalized structure of NB-• in the separated ion pair follows from the drastically shortened N−C bond and marked quinonoidal distortion of the benzenoid ring to signify complete (95%) electronic conjugation with the nitro substituent. On the other hand, the formation of contact ion pairs results in the substantial decrease of electronic conjugation in inverse order with cation size (K+ \u3e Rb+) owing to increased localization of negative charge from partial (NO2) bonding to the alkali-metal cation. Such a loss in electronic conjugation (or reverse charge transfer) may be counterintuitive, but it is in agreement with the distribution of odd-electron spin electron density from the ESR data and with the hypsochromic shift of the characteristic absorption band in the electronic spectra. Most importantly, this crystallographic study underscores the importance of ion-pair structure on the intrinsic property (and thus reactivity) of the component ions - as focused here on the nitrobenzenide anion

The route toward a diode-pumped 1-W erbium 3-µm fiber laser

A rate-equation analysis of the erbium 3-um ZBLAN fiber laser is performed. The computer calculation includes the longitudinal spatial resolution of the host material. It considers ground-state bleaching, excited-state absorption (ESA), interionic processes, lifetime quenching by co-doping, and stimulated emission at 2.7 um and 850 nm. State-of-the-art technology including double-clad diode pumping is assumed in the calculation. Pump ESA is identified as the major problem of this laser. With high Er3+ concentration, suitable Pr3+ co-doping, and low pump density, ESA is avoided and a diode-pumped erbium 3-um ZBLAN laser is predicted which is capable of emitting a transversely single-mode output power of 1.0 W when pumped with 7-W incident power at 800 nm. The corresponding output intensity which is relevant for surgical applications will be in the range of 1.8 MW/cm2. Compared to Ti:sapphire-pumped cascade-lasing regimes, the proposed approach represents a strong decrease of the requirements on mirror coatings, cavity alignment, and especially pump intensity. Of the possible drawbacks investigated in the simulation, only insufficient lifetime quenching is found to have a significant influence on laser performance

Dynamical properties of liquid Al near melting. An orbital-free molecular dynamics study

The static and dynamic structure of liquid Al is studied using the orbital free ab-initio molecular dynamics method. Two thermodynamic states along the coexistence line are considered, namely T = 943 K and 1323 K for which X-ray and neutron scattering data are available. A new kinetic energy functional, which fulfills a number of physically relevant conditions is employed, along with a local first principles pseudopotential. In addition to a comparison with experiment, we also compare our ab-initio results with those obtained from conventional molecular dynamics simulations using effective interionic pair potentials derived from second order pseudopotential perturbation theory.Comment: 15 pages, 12 figures, 2 tables, submitted to PR