Interpolating moving least-squares methods for fitting potential energy surfaces: computing high-density potential energy surface data from low-density ab initio data points

A highly accurate and efficient method for molecular global potential energy surface (PES) construction and fitting is demonstrated. An interpolating-moving-least-squares (IMLS)-based method is developed using low-density ab initio Hessian values to compute high-density PES parameters suitable for accurate and efficient PES representation. The method is automated and flexible so that a PES can be optimally generated for classical trajectories, spectroscopy, or other applications. Two important bottlenecks for fitting PESs are addressed. First, high accuracy is obtained using a minimal density of ab initio points, thus overcoming the bottleneck of ab initio point generation faced in applications of modified-Shepard-based methods. Second, high efficiency is also possible (suitable when a huge number of potential energy and gradient evaluations are required during a trajectory calculation). This overcomes the bottleneck in high-order IMLS-based methods, i.e., the high cost/accuracy ratio for potential energy evaluations. The result is a set of hybrid IMLS methods in which high-order IMLS is used with low-density ab initio Hessian data to compute a dense grid of points at which the energy, Hessian, or even high-order IMLS fitting parameters are stored. A series of hybrid methods is then possible as these data can be used for neural network fitting, modified-Shepard interpolation, or approximate IMLS. Results that are indicative of the accuracy, efficiency, and scalability are presented for one-dimensional model potentials as well as for three-dimensional (HCN) and six-dimensional (HOOH) molecular PESs.     

Low energy 13C+ and 13C2+ ion irradiation of water ice

In this paper we report the results of the first experimental study of the irradiation of low temperature water ice (30 and 90 K) using low energy (4 keV) 13C+ and 13C2+ ions. 13CO(2) and H2O(2) were readily formed within the H2O ice with the product yield and growth rate observed to be highly dependent on both the sample temperature and ion charge state.     

Efficient implicit algorithm for the equations of 2-D viscous compressible flow: application to shock-boundary layer interaction

A fully implicit algorithm has been developed to time integrate the equations of 2-D compressible viscous flow. The algorithm was constructed so as to optimize computational efficiency. The time-consuming block matrix inversions usually associated with implicit algorithms have been reduced to the trivial non-iterative inversion of four sets of scalar bidiagonal matrices. Thus, the algorithm requires virtually no more computer storage than an explicit algorithm. The efficient structure of the implicit algorithm is reflected in comparative timings which slow that it requires only a factor of two more computer time per point per time step than a typical explicit algorithm. Therefore, the algorithm allows more economical solution of given flows than existing explicit methods and also allows more difficult problems to be attempted using available computer resources. Application of the algorithm to the problem of shock-boundary layer interaction produces results consistent with both experimental measurements and other calculations.     

Regimes of frictional sliding of a spring-block system

In the context of rate-and-state friction, we revisit the crossover between the creep and inertial regimes in the dynamics of a spring-block system as observed and described in the dry friction experiment of Heslot et al. (1994) and Baumberger et al. (1994). We show that the transition between the quasi-static motion of a spring-block and its dynamic motion occurs at a lower sliding velocity than that which minimises the steady-state friction coefficient. We perform a weakly nonlinear stability analysis combined with numerical studies with the continuation package Auto. In particular, attention is focused on the change of nature the Hopf bifurcation from supercritical to subcritical, as observed by Heslot et al. Comparing the results obtained for different friction laws, we conclude that the weakly nonlinear analysis provides a possible criterion for distinguishing which friction laws may be physically relevant.     

Communication: highly accurate ozone formation potential and implications for kinetics

Atmospheric ozone is formed by the O + O(2) exchange reaction followed by collisional stabilization of the O(3)(?) intermediate. The dynamics of the O + O(2) reaction and to a lesser extent the O(3) stabilization depend sensitively on the underlying potential energy surface, particularly in the asymptotic region. Highly accurate Davidson corrected multi-state multi-reference configuration interaction calculations reported here reveal that the minimal energy path for the formation of O(3) from O + O(2) is a monotonically decaying function of the atom-diatom distance and contains no "reef" feature found in previous ab initio calculations. The absence of a submerged barrier leads to an exchange rate constant with the correct temperature dependence and is in better agreement with experiment, as shown by quantum scattering calculations.     

Direct observation of optical precursors in a region of anomalous dispersion

We create optical precursors by propagating a step-modulated optical pulse through a linear resonant dielectric absorber. The field emerging from the dielectric consists of a several-nanosecond-long spike with near 100% transmission, which decays to a constant value expected from Beer's law. This high-transmission spike might be useful for imaging applications requiring penetrating optical radiation. We compare our observations to two different theories, revealing that the spike consists of both the Sommerfeld and Brillouin precursors.     

Predicting turbulent flow in a staggered tube bundle

This paper presents the results of calculations performed for the turbulent, incompressible flow around a staggered array of tubes for which carefully obtained experimental results are available as part of an established ERCOFTAC-IAHR test case. The Reynolds-averaged Navier–Stokes equations are solved using a pressure-based finite volume algorithm, using collocated cell vertex store on an unstructured and adaptive mesh of tetrahedra. Turbulence closure is obtained with a truncated form of a low-Reynolds number k– model developed by Yang and Shih. The computational domain covers all seven rows of tubes used in the experimental study and periodic flow is allowed to develop naturally. The results of the computations are surprisingly good and compare favourably with results obtained by others using a wide range of alternative k– models for a single cylinder with periodic inflow and outflow boundaries on structured meshes.     

Wave-modulated orbits in rate-and-state friction

A frictional spring-block system has been widely used historically as a model to display some of the features of two slabs in sliding frictional contact. Putelat et al. (2008) [7] demonstrated that equations governing the sliding of two slabs could be approximated by spring-block equations, and studied relaxation oscillations for two slabs driven by uniform relative motion at their outer surfaces, employing this approximation. The present work revisits this problem. The equations of motion are first formulated exactly, with full allowance for wave reflections. Since the sliding is restricted to be independent of position on the interface, this leads to a set of differential-difference equations in the time domain. Formal but systematic asymptotic expansions reduce the equations to differential equations. Truncation of the differential system at the lowest non-trivial order reproduces a classical spring-block system, but with a slightly different “equivalent mass” than was obtained in the earlier work. Retention of the next term gives a new system, of higher order, that contains also some explicit effects of wave reflections. The smooth periodic orbits that result from the spring-block system in the regime of instability of steady sliding are “decorated” by an oscillation whose period is related to the travel time of the waves across the slabs. The approximating differential system reproduces this effect with reasonable accuracy when the mean sliding velocity is not too far from the critical velocity for the steady state. The differential system also displays a period-doubling bifurcation as the mean sliding velocity is increased, corresponding to similar behaviour of the exact differential-difference system.     

Low temperature rate constants for the N + CN → N(2) + C reaction: two-dimensional quantum capture calculations on an accurate potential energy surface

The title reaction is thought to be responsible for the production of molecular nitrogen in interstellar clouds. In this work, we report quantum capture calculations on a new two-dimensional potential energy surface determined by interpolating high-level ab initio data. The low-temperature rate constant calculated using a capture model is quite large and has a positive temperature dependence, in agreement with a recent experiment. The origin of the aforementioned behaviors of the rate constant is analyzed.     

Solution of sparse quasi-square rectangular systems by Gaussian elimination

We present a general method for the linear least-squares solutionof overdetermined and underdetermined systems. The method isparticularly efficient when the coefficient matrix is quasi-square,that is when the number of rows and number of columns is almostthe same. The numerical methods for linear least-squares problemsand minimum-norm solutions do not generally take account ofthis special characteristic. The proposed method is based onLU factorization of the original quasi-square matrix A, assumingthat A has full rank. In the overdetermined case, the LU factorsare used to compute a basis for the null space of A^T. The right-handside vector b is then projected onto this subspace and the least-squaressolution is obtained from the solution of this reduced problem.In the case of underdetermined systems, the desired solutionis again obtained through the solution of a reduced system.The use of this method may lead to important savings in computationaltime for both dense and sparse matrices. It is also shown inthe paper that, even in cases where the matrices are quite small,sparse solvers perform better than dense solvers. Some practicalexamples that illustrate the use of the method are included.