Quantum Monte Carlo Study of High Pressure Solid Molecular Hydrogen

We use the diffusion quantum Monte Carlo (DMC) method to calculate the ground state phase diagram of solid molecular hydrogen and examine the stability of the most important insulating phases relative to metallic crystalline molecular hydrogen. We develop a new method to account for finite-size errors by combining the use of twist-averaged boundary conditions with corrections obtained using the Kwee-Zhang-Krakauer (KZK) functional in density functional theory. To study band-gap closure and find the metallization pressure, we perform accurate quasi-particle many-body calculations using the $GW$ method. In the static approximation, our DMC simulations indicate a transition from the insulating Cmca-12 structure to the metallic Cmca structure at around 375 GPa. The $GW$ band gap of Cmca-12 closes at roughly the same pressure. In the dynamic DMC phase diagram, which includes the effects of zero-point energy, the Cmca-12 structure remains stable up to 430 GPa, well above the pressure at which the $GW$ band gap closes. Our results predict that the semimetallic state observed experimentally at around 360 GPa [Phys. Rev. Lett. {\bf 108}, 146402 (2012)] may correspond to the Cmca-12 structure near the pressure at which the band gap closes. The dynamic DMC phase diagram indicates that the hexagonal close packed $P6_3/m$ structure, which has the largest band gap of the insulating structures considered, is stable up to 220 GPa. This is consistent with recent X-ray data taken at pressures up to 183 GPa [Phys. Rev. B {\bf 82}, 060101(R) (2010)], which also reported a hexagonal close packed arrangement of hydrogen molecules

The Einstein-de Haas effect in an Fe_{15} cluster

Classical models of spin-lattice coupling are at present unable to accurately reproduce results for numerous properties of ferromagnetic materials, such as heat transport coefficients or the sudden collapse of the magnetic moment in hcp-Fe under pressure. This failure has been attributed to the absence of a proper treatment of effects that are inherently quantum mechanical in nature, notably spin-orbit coupling. This paper introduces a time-dependent, non-collinear tight binding model, complete with spin-orbit coupling and vector Stoner exchange terms, that is capable of simulating the Einstein-de Haas effect in a ferromagnetic Fe15 cluster. The tight binding model is used to investigate the adiabaticity timescales that determine the response of the orbital and spin angular momenta to a rotating, externally applied Β field, and we show that the qualitative behaviours of our simulations can be extrapolated to realistic timescales by use of the adiabatic theorem. An analysis of the trends in the torque contributions with respect to the field strength demonstrates that SOC is necessary to observe a transfer of angular momentum from the electrons to the nuclei at experimentally realistic Β fields. The simulations presented in this paper demonstrate the Einstein-de Haas effect from first principles using a Fe cluster

A new multi-center approach to the exchange-correlation interactions in ab initio tight-binding methods

A new approximate method to calculate exchange-correlation contributions in the framework of first-principles tight-binding molecular dynamics methods has been developed. In the proposed scheme on-site (off-site) exchange-correlation matrix elements are expressed as a one-center (two-center) term plus a {\it correction} due to the rest of the atoms. The one-center (two-center) term is evaluated directly, while the {\it correction} is calculated using a variation of the Sankey-Niklewski \cite{Sankey89} approach generalized for arbitrary atomic-like basis sets. The proposed scheme for exchange-correlation part permits the accurate and computationally efficient calculation of corresponding tight-binding matrices and atomic forces for complex systems. We calculate bulk properties of selected transition (W,Pd), noble (Au) or simple (Al) metals, a semiconductor (Si) and the transition metal oxide Ti$O_2$ with the new method to demonstrate its flexibility and good accuracy.Comment: 17 pages, 5 figure

Isotope effect in superconductors with coexisting interactions of phonon and nonphonon mechanisms

We examine the isotope effect of superconductivity in systems with coexisting interactions of phonon and nonphonon mechanisms in addition to the direct Coulomb interaction. The interaction mediated by the spin fluctuations is discussed as an example of the nonphonon interaction. Extended formulas for the transition temperature Tc and the isotope-effect coefficient alpha are derived for cases (a) omega_np omega_D, where omega_np is an effective cutoff frequency of the nonphonon interaction that corresponds to the Debye frequency omega_D in the phonon interaction. In case (a), it is found that the nonphonon interaction does not change the condition for the inverse isotope effect, i.e., mu^* > lambda_ph/2, but it modifies the magnitude of alpha markedly. In particular, it is found that a giant isotope shift occurs when the phonon and nonphonon interactions cancel each other largely. For instance, strong critical spin fluctuations may give rise to the giant isotope effect. In case (b), it is found that the inverse isotope effect occurs only when the nonphonon interaction and the repulsive Coulomb interaction, in total effect, work as repulsive interactions against the superconductivity. We discuss the relevance of the present result to some organic superconductors, such as kappa-(ET)2Cu(NCS)2 and Sr2RuO4 superconductors, in which inverse isotope effects have been observed, and briefly to high-Tc cuprates, in which giant isotope effects have been observed.Comment: 4 pages, 2 figures, (with jpsj2.cls, ver.1.2), v2:linguistic correction

Variational quantum Monte Carlo calculations for solid surfaces

Quantum Monte Carlo methods have proven to predict atomic and bulk properties of light and non-light elements with high accuracy. Here we report on the first variational quantum Monte Carlo (VMC) calculations for solid surfaces. Taking the boundary condition for the simulation from a finite layer geometry, the Hamiltonian, including a nonlocal pseudopotential, is cast in a layer resolved form and evaluated with a two-dimensional Ewald summation technique. The exact cancellation of all Jellium contributions to the Hamiltonian is ensured. The many-body trial wave function consists of a Slater determinant with parameterized localized orbitals and a Jastrow factor with a common two-body term plus a new confinement term representing further variational freedom to take into account the existence of the surface. We present results for the ideal (110) surface of Galliumarsenide for different system sizes. With the optimized trial wave function, we determine some properties related to a solid surface to illustrate that VMC techniques provide standard results under full inclusion of many-body effects at solid surfaces.Comment: 9 pages with 2 figures (eps) included, Latex 2.09, uses REVTEX style, submitted to Phys. Rev.

Enhancement of the upper critical field and a field-induced superconductivity in antiferromagnetic conductors

We propose a mechanism by which the paramagnetic pair-breaking effect is largely reduced in superconductors with coexisting antiferromagnetic long- range and short-range orders. The mechanism is an extension of the Jaccarino and Peter mechanism to antiferromagnetic conductors, but the resultant phase diagram is quite different. In order to illustrate the mechanism, we examine a model which consists of mobile electrons and antiferromagnetically correlated localized spins with Kondo coupling between them. It is found that for weak Kondo coupling, the superconductivity occurs over an extraordinarily wide region of the magnetic field including zero field. The critical field exceeds the Chandrasekhar and Clogston limit, but there is no lower limit in contrast to the Jaccarino and Peter mechanism. On the other hand, for strong Kondo coupling, both the low-field superconductivity and a field-induced superconductivity occur. Possibilities in hybrid ruthenate cuprate superconductors and some organic superconductors are discussed.Comment: 5 pages, 1 figure, revtex.sty, to be published in J.Phys.Soc.Jpn. Vol.71, No.3 (2002

Efficient Recursion Method for Inverting Overlap Matrix

A new O(N) algorithm based on a recursion method, in which the computational effort is proportional to the number of atoms N, is presented for calculating the inverse of an overlap matrix which is needed in electronic structure calculations with the the non-orthogonal localized basis set. This efficient inverting method can be incorporated in several O(N) methods for diagonalization of a generalized secular equation. By studying convergence properties of the 1-norm of an error matrix for diamond and fcc Al, this method is compared to three other O(N) methods (the divide method, Taylor expansion method, and Hotelling's method) with regard to computational accuracy and efficiency within the density functional theory. The test calculations show that the new method is about one-hundred times faster than the divide method in computational time to achieve the same convergence for both diamond and fcc Al, while the Taylor expansion method and Hotelling's method suffer from numerical instabilities in most cases.Comment: 17 pages and 4 figure