Wave functions for the methane molecule

If the potential field due to the nuclei in the methane molecule is expanded in terms of a set of spherical harmonics about the carbon nucleus, only the terms involving s, f, and higher harmonic functions differ from zero in the equilibrium configuration. Wave functions have been calculated for the equilibrium configuration, first including only the spherically symmetric s term in the potential, and secondly including both the s and the f terms. In the first calculation the complete Hartree-Fock S.C.F. wave functions were determined; in the second calculation a variation method was used to determine the best form of the wave function involving f harmonics. The resulting wave functions and electron density functions are presented and discussed

Approximation by harmonic polynomials in star-shaped domains and exponential convergence of Trefftz hp-dGFEM

We study the approximation of harmonic functions by means of harmonic polynomials in two-dimensional, bounded, star-shaped domains. Assuming that the functions possess analytic extensions to a delta-neighbourhood of the domain, we prove exponential convergence of the approximation error with respect to the degree of the approximating harmonic polynomial. All the constants appearing in the bounds are explicit and depend only on the shape-regularity of the domain and on delta. We apply the obtained estimates to show exponential convergence with rate O(exp(−b square root N)), N being the number of degrees of freedom and b>0, of a hp-dGFEM discretisation of the Laplace equation based on piecewise harmonic polynomials. This result is an improvement over the classical rate O(exp(−b cubic root N )), and is due to the use of harmonic polynomial spaces, as opposed to complete polynomial spaces.

The structure of crystallisable copolymers of L-lactide, epsilon-caprolactone and glycolide

We apply a new X-ray scattering approach to the study of melt-spun filaments of tri-block and random terpolymers prepared from lactide, caprolactone and glycolide. Both terpolymers contain random sequences, in both cases the overall fraction of lactide units is similar to 0.7 and C-13 and H-1 NMR shows the lactide sequence length to be similar to 9-10. A novel representation of the X-ray fibre pattern as series of spherical harmonic functions considerably facilitates the comparison of the scattering from the minority crystalline phase with hot drawn fibres prepared from the poly(L-lactide) homopolymer. Although the fibres exhibit rather disordered structures we show that the crystal structure is equivalent to that displayed by poly(L-lactide) for both the block and random terpolymers. There are variations in the development of a two-phase structure which reflect the differences in the chain architectures. There is evidence that the random terpolymer includes non-lactide units in to the crystal interfaces to achieve a well defined two-phase structure. (c) 2005 Published by Elsevier Ltd.

Vekua theory for the Helmholtz operator

Vekua operators map harmonic functions defined on domain in \mathbb R2R2 to solutions of elliptic partial differential equations on the same domain and vice versa. In this paper, following the original work of I. Vekua (Ilja Vekua (1907–1977), Soviet-Georgian mathematician), we define Vekua operators in the case of the Helmholtz equation in a completely explicit fashion, in any space dimension N ≥ 2. We prove (i) that they actually transform harmonic functions and Helmholtz solutions into each other; (ii) that they are inverse to each other; and (iii) that they are continuous in any Sobolev norm in star-shaped Lipschitz domains. Finally, we define and compute the generalized harmonic polynomials as the Vekua transforms of harmonic polynomials. These results are instrumental in proving approximation estimates for solutions of the Helmholtz equation in spaces of circular, spherical, and plane waves.

Analytical potentials for triatomic molecules IX. The prediction of anharmonic force constants from potential energy surfaces based on harmonic force fields and dissociation energies for SO2 and O3

Analytical potential energy functions which are valid at all dissociation limits have been derived for the ground states of SO2 and O3. The procedure involves minimizing the errors between the observed vibrational spectra and spectra calculated by a variational procedure. Good agreement is obtained between the observed and calculated spectra for both molecules. Comparisons are made between anharmonic force fields, previously determined from the spectral data, and the force fields obtained by differentiating the derived analytical functions at the equilibrium configurations.

An Exponentially Convergent Nonpolynomial Finite Element Method for Time-Harmonic Scattering from Polygons

In recent years nonpolynomial finite element methods have received increasing attention for the efficient solution of wave problems. As with their close cousin the method of particular solutions, high efficiency comes from using solutions to the Helmholtz equation as basis functions. We present and analyze such a method for the scattering of two-dimensional scalar waves from a polygonal domain that achieves exponential convergence purely by increasing the number of basis functions in each element. Key ingredients are the use of basis functions that capture the singularities at corners and the representation of the scattered field towards infinity by a combination of fundamental solutions. The solution is obtained by minimizing a least-squares functional, which we discretize in such a way that a matrix least-squares problem is obtained. We give computable exponential bounds on the rate of convergence of the least-squares functional that are in very good agreement with the observed numerical convergence. Challenging numerical examples, including a nonconvex polygon with several corner singularities, and a cavity domain, are solved to around 10 digits of accuracy with a few seconds of CPU time. The examples are implemented concisely with MPSpack, a MATLAB toolbox for wave computations with nonpolynomial basis functions, developed by the authors. A code example is included.

Extension of explicit formulas in Poissonian white noise analysis using harmonic analysis on configuration spaces

Harmonic analysis on configuration spaces is used in order to extend explicit expressions for the images of creation, annihilation, and second quantization operators in L2-spaces with respect to Poisson point processes to a set of functions larger than the space obtained by directly using chaos expansion. This permits, in particular, to derive an explicit expression for the generator of the second quantization of a sub-Markovian contraction semigroup on a set of functions which forms a core of the generator.

Error analysis of Trefftz-discontinuous Galerkin methods for the time-harmonic Maxwell equations

In this paper, we extend to the time-harmonic Maxwell equations the p-version analysis technique developed in [R. Hiptmair, A. Moiola and I. Perugia, Plane wave discontinuous Galerkin methods for the 2D Helmholtz equation: analysis of the p-version, SIAM J. Numer. Anal., 49 (2011), 264-284] for Trefftz-discontinuous Galerkin approximations of the Helmholtz problem. While error estimates in a mesh-skeleton norm are derived parallel to the Helmholtz case, the derivation of estimates in a mesh-independent norm requires new twists in the duality argument. The particular case where the local Trefftz approximation spaces are built of vector-valued plane wave functions is considered, and convergence rates are derived.

Variability of the Atlantic thermohaline circulation described by three-dimensional empirical orthogonal functions

We describe the use of bivariate 3d empirical orthogonal functions (EOFs) in characterising low frequency variability of the Atlantic thermohaline circulation (THC) in the Hadley Centre global climate model, HadCM3. We find that the leading two modes are well correlated with an index of the meridional overturning circulation (MOC) on decadal timescales, with the leading mode alone accounting for 54% of the decadal variance. Episodes of coherent oscillations in the sub-space of the leading EOFs are identified; these episodes are of great interest for the predictability of the THC, and could indicate the existence of different regimes of natural variability. The mechanism identified for the multi-decadal variability is an internal ocean mode, dominated by changes in convection in the Nordic Seas, which lead the changes in the MOC by a few years. Variations in salinity transports from the Arctic and from the North Atlantic are the main feedbacks which control the oscillation. This mode has a weak feedback onto the atmosphere and hence a surface climatic influence. Interestingly, some of these climate impacts lead the changes in the overturning. There are also similarities to observed multi-decadal climate variability.

A collocation method for high frequency scattering by convex polygons

We consider the problem of scattering of a time-harmonic acoustic incident plane wave by a sound soft convex polygon. For standard boundary or finite element methods, with a piecewise polynomial approximation space, the computational cost required to achieve a prescribed level of accuracy grows linearly with respect to the frequency of the incident wave. Recently Chandler–Wilde and Langdon proposed a novel Galerkin boundary element method for this problem for which, by incorporating the products of plane wave basis functions with piecewise polynomials supported on a graded mesh into the approximation space, they were able to demonstrate that the number of degrees of freedom required to achieve a prescribed level of accuracy grows only logarithmically with respect to the frequency. Here we propose a related collocation method, using the same approximation space, for which we demonstrate via numerical experiments a convergence rate identical to that achieved with the Galerkin scheme, but with a substantially reduced computational cost.