Searching for globally optimal functional forms for interatomic potentials using genetic programming with parallel tempering

Molecular dynamics and other molecular simulation methods rely on a potential energy function, based only on the relative coordinates of the atomic nuclei. Such a function, called a force field, approximately represents the electronic structure interactions of a condensed matter system. Developing such approximate functions and fitting their parameters remains an arduous, time-consuming process, relying on expert physical intuition. To address this problem, a functional programming methodology was developed that may enable automated discovery of entirely new force-field functional forms, while simultaneously fitting parameter values. The method uses a combination of genetic programming, Metropolis Monte Carlo importance sampling and parallel tempering, to efficiently search a large space of candidate functional forms and parameters. The methodology was tested using a nontrivial problem with a well-defined globally optimal solution: a small set of atomic configurations was generated and the energy of each configuration was calculated using the Lennard-Jones pair potential. Starting with a population of random functions, our fully automated, massively parallel implementation of the method reproducibly discovered the original Lennard-Jones pair potential by searching for several hours on 100 processors, sampling only a minuscule portion of the total search space. This result indicates that, with further improvement, the method may be suitable for unsupervised development of more accurate force fields with completely new functional forms.     

Infrared spectra of ClCN+, ClNC+, and BrCN+ trapped in solid neon

When a mixture of ClCN or BrCN with a large excess of neon is codeposited at 4.3 K with a beam of neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting solid includes prominent absorptions of the uncharged isocyanide, ClNC or BrNC, and of the corresponding cation, ClCN+ or BrCN+. The NC-stretching fundamentals of the isocyanides trapped in solid neon lie close to the positions for their previously reported argon-matrix counterparts. The CN-stretching absorptions of ClCN+ and BrCN+ and the CCl-stretching absorption of ClCN+ appear very close to the gas-phase band centers. Absorptions of two overtones and one combination band of ClCN+ are identified. Reversible photoisomerization of ClCN+ to ClNC+ occurs. The two stretching vibrational fundamentals and several infrared and near infrared absorptions associated with electronic transitions of ClNC+ are observed. Minor infrared peaks are attributed to the vibrational fundamental absorptions of the CX and CX(+) species (X=Cl,Br).     

Interpolating moving least-squares methods for fitting potential energy surfaces: an application to the H2CN unimolecular reaction

Classical trajectories have been used to compute rates for the unimolecular reaction H2CN-->H+HCN on a fitted ab initio potential energy surface (PES). The ab initio energies were obtained from CCSD(T)/aug-cc-pvtz electronic structure calculations. The ab initio energies were fitted by the interpolating moving least-squares (IMLS) method. This work continues the development of the IMLS method for producing ab initio PESs for use in molecular dynamics simulations of many-atom systems. A dual-level scheme was used in which the preliminary selection of data points was done using a low-level theory and the points used for fitting the final PES were obtained at the desired higher level of theory. Classical trajectories were used on various low-level IMLS fits to tune the fit to the unimolecular reaction under study. Procedures for efficiently picking data points, selecting basis functions, and defining cutoff limits to exclude distant points were investigated. The accuracy of the fitted PES was assessed by comparing interpolated values of quantities to the corresponding ab initio values. With as little as 330 ab initio points classical trajectory rate constants were converged to 5%-10% and the rms error over the six-dimensional region sampled by the trajectories was a few tenths of a kcal/mol.     

Unsteady flow around impacting bluff bodies

The flow resulting from the collision without rebound of generic bluff bodies with a wall in a still viscous fluid is investigated both computationally and experimentally. Emphasis is on the case of a circular cylinder impact (two-dimensional geometry), but comparisons with the flow generated by the impact of a sphere (axisymmetric geometry) are included. For normal cylinder impacts, the two counter-rotating vortices forming behind the body during its motion continue their trajectory towards the wall after the collision, leading to the generation of opposite-signed secondary vorticity at the cylinder and wall surfaces. Secondary vortices forming from this vorticity at higher Reynolds numbers exhibit a short-wavelength three-dimensional instability. Comparison with the sphere impact reveals significant differences in the scales of the vortices after the collision, due to the additional vortex stretching acting in the axisymmetric geometry. This leads to a delay in the onset of three-dimensionality and to a different instability mechanism. Oblique cylinder impacts are also considered. For increasing impact angles, the wall effect is gradually reduced on one side of the cylinder, which favours the roll-up of the secondary vorticity and increases the rebound height of the vortex system.     

Mixed-mode interface toughness of wafer-level Cu-Cu bonds using asymmetric chevron test

Characterization of interfacial adhesion is critical for the development of wafer bonding processes to manufacture microsystems with high yield and reliability. It is imperative that the test method used in such adhesion studies corresponds to the loading conditions present during processing and operation of the devices. In most applications in which wafers and die are bonded, the interface experiences a combination of shear and normal loading (i.e. mixed-mode loading) with the relative magnitude of the Mode I and II components varying in different scenarios. In the current work, the toughness of Cu-Cu thermocompression bonds, which are of interest for the fabrication of three-dimensional integrated circuits, is analyzed using a bonded chevron specimen with layers of different thickness that allows for the application of interfacial loading with variable mode mixity. The phase angle (a function of the degree of mode mixity at the interface) is varied from 0° to 24° by changing the layer thickness ratio from 1 to 0.48. The Cu-Cu bond toughness increases from 2.68 to 10.1 J/m², as the loading is changed from Mode I (pure tension) to a loading with a phase angle of 24°. The energy of plastic dissipation increases with increasing mode mixity, resulting in the enhanced interface toughness. The Mode I toughness of Cu-Cu bonds is minimally affected by plasticity, and therefore, provides the closest estimate of the interfacial work of fracture under the bonding conditions employed.     

Dependence of diffusive permeation rates and selectivities on upstream and downstream pressures : IV. Computer simulation of nonideal systems

In previous papers we have shown that a semi-empirical thermodynamic—diffusive model appears to duplicate the behavior of the hexane/heptane/polyethylene system with regard to the effect of upstream and downstream pressure on rate and separation. In the present paper we present a numerical method for dealing with our model equations, which allows us to treat nonideal systems, and to make use of more general expressions describing the concentration dependence of diffusivity. This method is discussed in detail, and several typical simulation results are presented.     

Towards antihydrogen confinement with the ALPHA antihydrogen trap

ALPHA is an international project that has recently begun experimentation at CERN’s Antiproton Decelerator (AD) facility. The primary goal of ALPHA is stable trapping of cold antihydrogen atoms with the ultimate goal of precise spectroscopic comparisons with hydrogen. We discuss the status of the ALPHA project and the prospects for antihydrogen trapping.