Wavefunctions and Correlation Energies for Two‐, Three‐, and Four‐Electron Atoms

A recently developed method (the GF method) which is equivalent to optimizing the orbitals of a Slater determinant after spin projection has been applied to H^−, He, Li^+, Be^++, Li, Be^+,B^++, Li^−, Be, B^+ and C^++. These wavefunctions, which can be given an independent particle interpretation, yield better energies than those of the Hartree‐Fock method. For example, H^− and Li^− are correctly predicted to be stable in contradistinction with the Hartree‐Fock results. The new correlation energies are tabulated and compared to the Hartree‐Fock values. In the case of the two‐electron systems the new wavefunctions are nearly at the radial limit, accounting for 93% to 97% of the radial correlation error present in the Hartree‐Fock description

Microscopic mechanism of water diffusion in glucose glasses

The preservation of biomaterials depends critically on the mobility of water in the glassy state, manifested as a secondary beta relaxation and diffusion. We use coarse grain simulations to elucidate the molecular mechanism underlying the relaxations for water-glucose glass, finding two pathways for water diffusion: (i) water jumps into neighbor water positions (linking to water structure), and (ii) water jumps into glucose positions (coupling to glucose rotation). This work suggests strategies for enhancing preservation by stiffening the segmental motions of the carbohydrates

Ozone model for bonding of an O_2 to heme in oxyhemoglobin

Several rather different models of the Fe-O_2 bond in oxyhemoglobin have previously been proposed, none of which provide a satisfactory explanation of several properties. We propose a new model for the bonding of an O_2 to the Fe of myoglobin and hemoglobin and report ab initio generalized valence bond and configuration interaction calculations on FeO_2 that corroborate this model. Our model is based closely upon the bonding in ozone which recent theoretical studies have shown to be basically a biradical with a singlet state stabilized by a three-center four-electron pi bond. In this model, the facile formation and dissociation of the Fe-O_2 bond is easily rationalized since the O_2 always retains its triplet ground state character. The ozone model leads naturally to a large negative electric field gradient (in agreement with Mossbauer studies) and to z-polarized (perpendicular to the heme) charge transfer transitions. It also suggests that the 1.3 eV transition, present in HbO_2 and absent in HbCO, is due to a porphyrin-to-Fe transition, analogous to that of ferric hemoglobins (e.g., HbCN)

Universal Properties of Cuprate Superconductors: T_c Phase Diagram, Room-Temperature Thermopower, Neutron Spin Resonance, and STM Incommensurability Explained in Terms of Chiral Plaquette Pairing

We report that four properties of cuprates and their evolution with doping are consequences of simply counting four-site plaquettes arising from doping, (1) the universal T_c phase diagram (superconductivity between ~0.05 and ~0.27 doping per CuO_2 plane and optimal T_c at ~0.16), (2) the universal doping dependence of the room-temperature thermopower, (3) the superconducting neutron spin resonance peak (the “41 meV peak”), and (4) the dispersionless scanning tunneling conductance incommensurability. Properties (1), (3), and (4) are explained with no adjustable parameters, and (2) is explained with exactly one. The successful quantitative interpretation of four very distinct aspects of cuprate phenomenology by a simple counting rule provides strong evidence for four-site plaquette percolation in these materials. This suggests that inhomogeneity, percolation, and plaquettes play an essential role in cuprates. This geometric analysis may provide a useful guide to search for new compositions and structures with improved superconducting properties

Study of surfaces and interfaces using quantum chemistry techniques

There are a number of difficulties in elucidating the microscopic details of the electronic states at surfaces and interfaces. The first step should be to determine the structure at the surface or interface, but this is difficult experimentally even for the clean, ordered surface and extremely difficult for cases with impurity atoms (e.g., nonordered oxide layers). The theoretical study of such geometries and energy surfaces is the subject of quantum chemistry. We present a review of some of the theoretical techniques from quantum chemistry that are being applied to surfaces. The procedure consists of treating a finite piece of the surface or interface as a molecule. Ab initio calculations are then carried out on the molecule using the generalized valence bond (GVB) method (with additional configuration interaction), thereby incorporating the dominant many‐body effects. The reliability of these techniques is discussed by giving some examples from molecular chemistry and the surfaces of solids. The strengths and weaknesses of this approach are compared with more traditional band theory related methods and are illustrated with various examples

Catalytic role of boron atoms in self-interstitial clustering in Si

Using density functional theory (DFT) calculations and kinetic simulations, we have investigated the influence of boron atoms on self-interstitial clustering in Si. From DFT calculations of neutral interstitial clusters with a single B atom (BsIn, nIn–1 + BsI) becomes substantially weaker than that of an interstitial (BsIn-->BsIn–1 + I) when n>=4. This implies boron can be liberated while leaving an interstitial cluster behind. Our kinetic simulations including the boron liberation explain well experimental observations reported by J. L. Benton et al., J. Appl. Phys. 82, 120 (1997)