Acceleration Schemes for Ab-Initio Molecular Dynamics and Electronic Structure Calculations

We study the convergence and the stability of fictitious dynamical methods for electrons. First, we show that a particular damped second-order dynamics has a much faster rate of convergence to the ground-state than first-order steepest descent algorithms while retaining their numerical cost per time step. Our damped dynamics has efficiency comparable to that of conjugate gradient methods in typical electronic minimization problems. Then, we analyse the factors that limit the size of the integration time step in approaches based on plane-wave expansions. The maximum allowed time step is dictated by the highest frequency components of the fictitious electronic dynamics. These can result either from the large wavevector components of the kinetic energy or from the small wavevector components of the Coulomb potential giving rise to the so called {\it charge sloshing} problem. We show how to eliminate large wavevector instabilities by adopting a preconditioning scheme that is implemented here for the first-time in the context of Car-Parrinello ab-initio molecular dynamics simulations of the ionic motion. We also show how to solve the charge-sloshing problem when this is present. We substantiate our theoretical analysis with numerical tests on a number of different silicon and carbon systems having both insulating and metallic character.Comment: RevTex, 9 figures available upon request, to appear in Phys. Rev.

Accurate evaluation of the interstitial KKR-Green function

It is shown that the Brillouin zone integral for the interstitial KKR-Green function can be evaluated accurately by taking proper care of the free-electron singularities in the integrand. The proposed method combines two recently developed methods, a supermatrix method and a subtraction method. This combination appears to provide a major improvement compared with an earlier proposal based on the subtraction method only. By this the barrier preventing the study of important interstitial-like defects, such as an electromigrating atom halfway along its jump path, can be considered as being razed.Comment: 23 pages, RevTe

van der Waals coefficients for positronium-atom interactions

The van der Waals coefficients for positronium interactions with a number of rare gases (He, Ne, Ar, Kr, and Xe) and alkali-metal atoms (Li, Na, K, and Rb) are estimated using a variety of ab initio and semiempirical methods. Dispersion coefficients are also presented for atomic hydrogen and a number of rare-gas and alkali-metal atoms for validation purposes

Multiple scattering theory for space filling potentials

Multiple scattering theory (MST) provides an efficient technique for solving the wave equation for the special case of muffin-tin potentials. Here MST is extended to treat space filling non-muffin tin potentials and its validity, accuracy and efficiency are tested by application of the two dimensional empty lattice test. For this test it is found that the traditional formulation of MST does not coverage as the number of partial waves is increased. A simple modification of MST, however, allows this problem to be solved exactly and efficiently. 15 refs., 3 tabs

The role of dynamical polarization of the ligand to metal charge transfer excitations in {\em ab initio} determination of effective exchange parameters

The role of the bridging ligand on the effective Heisenberg coupling parameters is analyzed in detail. This analysis strongly suggests that the ligand-to-metal charge transfer excitations are responsible for a large part of the final value of the magnetic coupling constant. This permits to suggest a new variant of the Difference Dedicated Configuration Interaction (DDCI) method, presently one of the most accurate and reliable for the evaluation of magnetic effective interactions. This new method treats the bridging ligand orbitals mediating the interaction at the same level than the magnetic orbitals and preserves the high quality of the DDCI results while being much less computationally demanding. The numerical accuracy of the new approach is illustrated on various systems with one or two magnetic electrons per magnetic center. The fact that accurate results can be obtained using a rather reduced configuration interaction space opens the possibility to study more complex systems with many magnetic centers and/or many electrons per center.Comment: 7 pages, 4 figure

A correlation energy calculation of the 1s hole state in neon

The Bethe-Goldstone formalism for calculating correlation energy has been applied to the 1s hole state in neon. The binding energy of the 1s electron is computed to be 870.0 eV which is in excellent agreement with experiment. © 1971.SCOPUS: ar.jinfo:eu-repo/semantics/publishe