The spontaneous ionization of a hydrogen atom in an electric field, 1

Numerical integration of spontaneous ionization of hydrogen atom in electric field using Schroedinger equatio

Optical excitations in organic molecules, clusters and defects studied by first-principles Green's function methods

Spectroscopic and optical properties of nanosystems and point defects are discussed within the framework of Green's function methods. We use an approach based on evaluating the self-energy in the so-called GW approximation and solving the Bethe-Salpeter equation in the space of single-particle transitions. Plasmon-pole models or numerical energy integration, which have been used in most of the previous GW calculations, are not used. Fourier transforms of the dielectric function are also avoided. This approach is applied to benzene, naphthalene, passivated silicon clusters (containing more than one hundred atoms), and the F center in LiCl. In the latter, excitonic effects and the $1s \to 2p$ defect line are identified in the energy-resolved dielectric function. We also compare optical spectra obtained by solving the Bethe-Salpeter equation and by using time-dependent density functional theory in the local, adiabatic approximation. From this comparison, we conclude that both methods give similar predictions for optical excitations in benzene and naphthalene, but they differ in the spectra of small silicon clusters. As cluster size increases, both methods predict very low cross section for photoabsorption in the optical and near ultra-violet ranges. For the larger clusters, the computed cross section shows a slow increase as function of photon frequency. Ionization potentials and electron affinities of molecules and clusters are also calculated.Comment: 9 figures, 5 tables, to appear in Phys. Rev. B, 200

Van der Waals forces in density functional theory: perturbational long-range electron interaction corrections

Long-range exchange and correlation effects, responsible for the failure of currently used approximate density functionals in describing van der Waals forces, are taken into account explicitly after a separation of the electron-electron interaction in the Hamiltonian into short- and long-range components. We propose a "range-separated hybrid" functional based on a local density approximation for the short-range exchange-correlation energy, combined with a long-range exact exchange energy. Long-range correlation effects are added by a second-order perturbational treatment. The resulting scheme is general and is particularly well-adapted to describe van der Waals complexes, like rare gas dimers.Comment: 8 pages, 1 figure, submitted to Phys. Rev.

Dynamical aspects of inextensible chains

In the present work the dynamics of a continuous inextensible chain is studied. The chain is regarded as a system of small particles subjected to constraints on their reciprocal distances. It is proposed a treatment of systems of this kind based on a set Langevin equations in which the noise is characterized by a non-gaussian probability distribution. The method is explained in the case of a freely hinged chain. In particular, the generating functional of the correlation functions of the relevant degrees of freedom which describe the conformations of this chain is derived. It is shown that in the continuous limit this generating functional coincides with a model of an inextensible chain previously discussed by one of the authors of this work. Next, the approach developed here is applied to a inextensible chain, called the freely jointed bar chain, in which the basic units are small extended objects. The generating functional of the freely jointed bar chain is constructed. It is shown that it differs profoundly from that of the freely hinged chain. Despite the differences, it is verified that in the continuous limit both generating functionals coincide as it is expected.Comment: 15 pages, LaTeX 2e + various packages, 3 figures. The title has been changed and three references have been added. A large part of the manuscript has been rewritten to improve readability. Chapter 4 has been added. It contains the construction of the generating functional without the shish-kebab approximation and a new derivation of the continuous limit of the freely jointed bar chai

Jahn Teller Effect of Cations in Water: The Cupric Ion in Water

We report a molecular dynamics model for the Jahn Teller effect in the solvation shell of a cation in solution in an aqueous liquid. We apply the model to the cupric ion and compare results with results of neutron scattering experiments on copper chlorate solutions. We conclude that the original interpretation of the experiments in terms of a Jan Teller effect may require modification

Theoretical study of O adlayers on Ru(0001)

Recent experiments performed at high pressures indicate that ruthenium can support unusually high concentrations of oxygen at the surface. To investigate the structure and stability of high coverage oxygen structures, we performed density functional theory calculations, within the generalized gradient approximation, for O adlayers on Ru(0001) from low coverage up to a full monolayer. We achieve quantitative agreement with previous low energy electron diffraction intensity analyses for the (2x2) and (2x1) phases and predict that an O adlayer with a (1x1) periodicity and coverage of 1 monolayer can form on Ru(0001), where the O adatoms occupy hcp-hollow sites.Comment: RevTeX, 6 pages, 4 figure

The rate-limiting step for alkane dehydrogenation in zeolite H-ZSM-5.

We have carried out a computational study of protolytic cracking, dehydrogenation, and H/D exchange of ethane, propane, and butane using a cluster model of H-ZSM-5. Our previous work has demonstrated that quantum-chemical techniques can give quantitatively accurate activation energies for alkane cracking in zeolites [1]. Experimental kinetic studies have shown that the apparent activation energies for cracking and H/D exchange decrease with n-alkane chain length, while for dehydrogenation the energies increase [2,3]. Our goal is to study the dependence of the activation energy on the alkane chain length in these reactions and to understand why the dehydrogenation reaction behaves so differently

Tomographic Separation of Composite Spectra. VIII. The Physical Properties of the Massive Compact Binary in the Triple Star System HD 36486 (delta Orionis A)

Double-lined spectroscopic orbital elements have recently been found for the central binary in the massive triple, delta Orionis A based on radial velocities from cross-correlation techniques applied to IUE high dispersion spectra and He I 6678 spectra obtained at Kitt Peak. The primary and secondary velocity amplitudes were found to be 94.9 +/- 0.6 km/s and 186 +/- 9 km/s respectively. Tomographic reconstructions of the primary and secondary stars' spectra confirm the O9.5 II classification of the primary and indicate a B0.5 III type for the secondary. The widths of the UV cross-correlation functions are used to estimate the projected rotational velocities, Vsin i = 157 +/- 6 km/s and 138 +/- 16 km/s for the primary and secondary, respectively implying that both stars rotate faster than their orbital motion. We used the spectroscopic results to make a constrained fit of the Hipparcos light curve of this eclipsing binary, and the model fits limit the inclination to the range between 67 and 77 degrees. The i = 67 degrees solution, which corresponds to a near Roche-filling configuration, results in a primary mass of 11.2 solar masses and a secondary mass of 5.6 solar masses, both of which are substantially below the expected masses for stars of their luminosity. This binary may have experienced a mass ratio reversal caused by Case A Roche lobe overflow, or the system may have suffered extensive mass loss through a binary interaction, perhaps during a common envelope phase, in which most of the primary's mass was lost from the system rather than transferred to the secondary.Comment: 27 pages, 15 figures in press, the Astrophysical Journal, February 1, 200

Electron affinities of the first- and second- row atoms: benchmark ab initio and density functional calculations

A benchmark ab initio and density functional (DFT) study has been carried out on the electron affinities of the first- and second-row atoms. The ab initio study involves basis sets of $spdfgh$ and $spdfghi$ quality, extrapolations to the 1-particle basis set limit, and a combination of the CCSD(T), CCSDT, and full CI electron correlation methods. Scalar relativistic and spin-orbit coupling effects were taken into account. On average, the best ab initio results agree to better than 0.001 eV with the most recent experimental results. Correcting for imperfections in the CCSD(T) method improves the mean absolute error by an order of magnitude, while for accurate results on the second-row atoms inclusion of relativistic corrections is essential. The latter are significantly overestimated at the SCF level; for accurate spin-orbit splitting constants of second-row atoms inclusion of (2s,2p) correlation is essential. In the DFT calculations it is found that results for the 1st-row atoms are very sensitive to the exchange functional, while those for second-row atoms are rather more sensitive to the correlation functional. While the LYP correlation functional works best for first-row atoms, its PW91 counterpart appears to be preferable for second-row atoms. Among ``pure DFT'' (nonhybrid) functionals, G96PW91 (Gill 1996 exchange combined with Perdew-Wang 1991 correlation) puts in the best overall performance. The best results overall are obtained with the 1-parameter hybrid modified Perdew-Wang (mPW1) exchange functionals of Adamo and Barone [J. Chem. Phys. {\bf 108}, 664 (1998)], with mPW1LYP yielding the best results for first-row, and mPW1PW91 for second-row atoms. Indications exist that a hybrid of the type $a$ mPW1LYP + $(1-a)$ mPW1PW91 yields better results than either of the constituent functionals.Comment: Phys. Rev. A, in press (revised version, review of issues concerning DFT and electron affinities added