Inelastic scattering with Chebyshev polynomials and preconditioned conjugate gradient minimization

We describe and test an implementation, using a basis set of Chebyshev polynomials, of a variational method for solving scattering problems in quantum mechanics. This minimum error method (MEM) determines the wave function Psi by minimizing the least-squares error in the function (H Psi - E Psi), where E is the desired scattering energy. We compare the MEM to an alternative, the Kohn variational principle (KVP), by solving the Secrest-Johnson model of two-dimensional inelastic scattering, which has been studied previously using the KVP and for which other numerical solutions are available. We use a conjugate gradient (CG) method to minimize the error, and by preconditioning the CG search, we are able to greatly reduce the number of iterations necessary; the method is thus faster and more stable than a matrix inversion, as is required in the KVP. Also, we avoid errors due to scattering off of the boundaries, which presents substantial problems for other methods, by matching the wave function in the interaction region to the correct asymptotic states at the specified energy; the use of Chebyshev polynomials allows this boundary condition to be implemented accurately. The use of Chebyshev polynomials allows for a rapid and accurate evaluation of the kinetic energy. This basis set is as efficient as plane waves but does not impose an artificial periodicity on the system. There are problems in surface science and molecular electronics which cannot be solved if periodicity is imposed, and the Chebyshev basis set is a good alternative in such situations.     

Wave Packet Approach to Adiabatic and Nonadiabatic Dynamics of Cold Inelastic Scatterings

Due to the extremely large de Broglie wavelength of cold molecules, cold inelastic scattering is always characterized by the time-independent close-coupling (TICC) method. However, the TICC method is difficult to apply to collisions of large molecular systems. Here, we present a new strategy for characterizing cold inelastic scattering using wave packet (WP) method. In order to deal with the long de Broglie wavelength of cold molecules, the total wave function is divided into interaction, asymptotic and long-range regions (IALR). The three regions use different numbers of ro-vibrational basis functions, especially the long-range region, which uses only one function corresponding to the initial ro-vibrational state. Thus, a very large grid range can be used to characterize long de Broglie wavelengths in scattering coordinates. Due to its better numerical scaling law, the IALR-WP method has great potential in studying the inelastic scatterings of larger collision systems at cold and ultracold regimes.     

On the number of spanning trees in alternating polycyclic chains

In this paper we generalize and unify results of several recent papers by presenting explicit formulas for the number of spanning trees in a class of unbranched polycyclic polymers. From these formulas we immediately deduce the asymptotic behavior of the number of spanning trees, and, as a consequence, we obtain combinatorial proofs of some identities for Chebyshev polynomials of the second kind.     

Bound and scattering states for a hyperbolic‐type potential in view of a new developed approximation

A new developed approximation is used to obtain the arbitrary l‐wave bound and scattering state solutions of Schrödinger equation for a particle in a hyperbolic‐type potential. For bound state, the energy eigenvalue equation and unnormalized wave functions in terms of Jacobi polynomials are achieved using the Nikiforov–Uvarov (NU) method. Besides, energy eigenvalues are calculated numerically for some states and compared with those given in the literature to check accuracy of our results. For scattering state, the wave function is found in terms of hypergeometric functions. Furthermore, scattering amplitude and phase shifts are achieved using scattering solutions. Also it is shown that the energy eigenvalue equation obtained from analytic property of scattering amplitude is same with one obtained using NU method. © 2015 Wiley Periodicals, Inc.     

Construction of an accurate quartic force field by using generalised least-squares fitting and experimental design

In this work we present an attractive least-squares fitting procedure which allows for the calculation of a quartic force field by jointly using energy, gradient, and Hessian data, obtained from electronic wave function calculations on a suitably chosen grid of points. We use the experimental design to select the grid points: a “simplex-sum” of Box and Behnken grid was chosen for its efficiency and accuracy. We illustrate the numerical implementations of the method by using the energy and gradient data for H₂O and H₂CO. The B3LYP/cc-pVTZ quartic force field performed from 11 and 44 simplex-sum configurations shows excellent agreement in comparison to the classical 44 and 168 energy calculations.     

The effect of ambient temperature on the propagation of nonadiabatic combustion waves

In this paper, we undertake an analytical and numerical investigation of the linear stability and properties of travelling nonadiabatic combustion wave for the case of nonzero ambient temperature. Here we consider premixed fuel with one-step exothermic reaction described by Arrhenius law. The speed of the front is estimated analytically by employing the matched asymptotic expansion approach and numerically using the shooting and relaxation methods. It is shown that increasing the ambient temperature results in the growth of both the flame speed and the region of existence of the travelling wave solutions in the parameter space. The linear stability of the travelling wave solution is investigated analytically by using the matched asymptotic expansion method and numerically by employing the Evans function approach. We demonstrate that by increasing the ambient temperature the stability of the propagating wave can also be increased.AMS subject classification: cation: 35K57, 80A25     

Atomic wave function forms

Using variational Monte Carlo, we compare the features of 118 trial wave function forms for selected ground and excited states of helium, lithium, and beryllium in order to determine which characteristics give the most rapid convergence toward the exact nonrelativistic energy. We find that fully antisymmetric functions are more accurate than are those which use determinants, that exponential functions are more accurate than are linear function, and that the Padé function is anomalously accurate for the two-electron atom. We also find that the asymptotic and nodal behavior of the atomic wave function is best described by a minimal set of functions. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1001–1022, 1997     

On the calculation of Rys polynomials and quadratures

A discretized Stieltjes procedure is used to generate Rys polynomials from a three-term recurrence relationship. We show that this process is numerically stable in contrast to the evaluation from the moments of the system and polynomial coefficients, i.e., the Stieltjes procedure, where numerical instabilities arise. Rys quadratures may thus be calculated in an accurate manner from the Rys polynomials generated via this discretized Stieltjes procedure.     

Properties of nearly one-electron molecules. I. An iterative Green function approach to calculating the reaction matrix

An ab initio R-matrix method for determining the molecular reaction matrix of scattering theory is introduced. The method makes use of a principal-value Green function to compute the collision channel wave functions for the scattered electron, in combination with the Kohn variational scheme for the evaluation of R-matrix eigenvalues on a spherical boundary surface at short range. This technique permits the size of the bounded volume in the variational calculation to be reduced, making the computations fast and efficient. The reaction matrix is determined in a form that minimizes its energy dependence. Thus the procedure does not require modification or an increase in the computational effort to study the electronic structure and dynamics in Rydberg molecules with extremely polar ion cores. The analysis is specialized to examine the bound-state and free-electron scattering properties of nearly one-electron molecular systems, which are characterized by a Rydberg/scattering electron incident on a closed-shell ion core. However, it is shown that the treatment is compatible with all-electron/ab initio representations of open-shell and nonlinear polyatomic ion cores, emphasizing its generality. The introduced approach is used to calculate the electronic spectrum of the calcium monofluoride molecule, which has the extremely polar (Ca+2F-)+e- closed-shell ion-core configuration. The calculation utilizes an effective single-electron potential determined by M. Arif, C. Jungen, and A. L. Roche [J. Chem. Phys. 106, 4102 (1997)] previously. Close agreement with experimental data is obtained. The results demonstrate the practical utility of this method as a viable alternative to the standard variational approaches.     

Analysis of a quasi-elastic laser scattering spectrum using the maximum entropy method.

We have applied the maximum entropy method (MEM) to the analysis of quasi-elastic laser scattering (QELS) spectra and have established a technique for determining capillary wave frequencies with a higher time resolution than that of the conventional procedure. Although the QELS method has an advantage in time resolution over mechanical methods, it requires the averaging of at least 20-100 power spectra for determining capillary wave frequencies. We find that the MEM analysis markedly improves the S/N ratio of the power spectra, and that averaging the spectra is not necessary for determining the capillary wave frequency, i.e., it can be estimated from one power spectrum. The time resolution of the QELS attains the theoretical limit by using MEM analysis.     

Reconciling semiclassical and Bohmian mechanics: IV. Multisurface dynamics

In previous articles (J. Chem. Phys. 2004, 121, 4501; 2006, 124, 034115; 2006, 124, 034116) a bipolar counter-propagating wave decomposition, Psi = Psi+ + Psi-, was presented for stationary states Psi of the one-dimensional Schr?dinger equation, such that the components Psi+/- approach their semiclassical WKB analogs in the large action limit. The corresponding bipolar quantum trajectories are classical-like and well-behaved, even when Psi has many nodes or is wildly oscillatory. In this paper, the method is generalized for multisurface scattering applications and applied to several benchmark problems. A natural connection is established between intersurface transitions and (+ <--> -) transitions.     

Improved scheme to solve the atomic Schrödinger equation in hyperspherical coordinates

An improved scheme to accelerate the convergence in the calculations of N-electron atoms, which is based on the exact method we proposed before in hyperspherical coordinates, is presented. The factors influencing the rate of convergence in both parts of expansions in wave function with the hyperspherical harmonics (HHs) of hyperangles and the generalized Laguerre polynomials (GLPs) of hyperradius were investigated. A reselected asymptotic term was introduced by including more structural features in it to accelerate the convergence in the expansion part with the HHs, and a transformation of the hyperradius was used to keep the convergence going properly in the expansion part with the GLPs. Calculations with this scheme for the helium atom were given and compared with some other ones. More accurate results were obtained by considering a simple cusp parameter. © 1996 John Wiley & Sons, Inc.     

Real-time linear response for time-dependent density-functional theory

We present a linear-response approach for time-dependent density-functional theories using time-adiabatic functionals. The resulting theory can be performed both in the time and in the frequency domain. The derivation considers an impulsive perturbation after which the Kohn-Sham orbitals develop in time autonomously. The equation describing the evolution is not strictly linear in the wave function representation. Only after going into a symplectic real-spinor representation does the linearity make itself explicit. For performing the numerical integration of the resulting equations, yielding the linear response in time, we develop a modified Chebyshev expansion approach. The frequency domain is easily accessible as well by changing the coefficients of the Chebyshev polynomial, yielding the expansion of a formal symplectic Green's operator.     

Moving boundary truncated grid method: Multidimensional quantum dynamics

The moving boundary truncated grid (TG) method is used to study wave packet dynamics of multidimensional quantum systems. As time evolves, appropriate Eulerian grid points required for propagating a wave packet are activated and deactivated with no advance information about the dynamics. This method is applied to the Henon-Heiles potential and wave packet barrier scattering in two, three, and four dimensions. Computational results demonstrate that the TG method not only leads to a great reduction in the number of grid points needed to perform accurate calculations but also is computationally more efficient than the full grid calculations.     

Analytic correlated wave functions in momentum space and related properties of helium like ions

We obtain analytic correlated wave functions in momentum space as the Fourier transform of correlated wave functions which are able to incorporate almost all of the correlation energy for the ground-state of two-electron atoms. Then we study the atomic momentum-density, the Compton profile and the elastic and inelastic scattering factors for this kind of wave functions. The scattering factors are also compared with the ones provided by a more accurate correlated wave function. All the calculations can be analytically performed, provided the correlated wave function in position space has been determined.     

Generation of the eigenvectors of the topological matrix from graph theory

The technique of describing the characteristic polynomial of a graph is here extended to construction of the eigenvectors. Recurrence relations and path tracing are combined to generate eigenvector coefficients as polynomial functions of the eigenvalues. The polynomials are expressed as linear functions of Chebyshev polynomials in order to simplify the computational effort. Particular applications to the Hückel MO theory, including heteroatom effects, are shown.     

The properties of off-shell coulomb radial wavefunctions

Approximations to exact wave functions for the scattering of few-particle systems often involve components corresponding to the interaction of two of the particles “off the energy-shell”. Several examples arising in the collision of ions and photons with atoms are given. An expansion in partial waves leads to an off-shell radial wave function. The defining differential equation is solved here numerically with particular emphasis on the behaviour arising from two-body potentials of long-range Coulomb form. The transition to shell of the radial wave functions, Jost functions and solutions andT-matrix elements is discussed for both short-range and Coulomb potentials. It is shown that the approximation of a Coulomb potential by a shorter-range form involves little error when sufficiently far off the energy shell.