Auxiliary-field quantum Monte Carlo study of first- and second-row post-d elements

A series of calculations for the first- and second-row post-d elements (Ga-Br and In-I) are presented using the phaseless auxiliary-field quantum Monte Carlo (AF QMC) method. This method is formulated in a Hilbert space defined by any chosen one-particle basis, and maps the many-body problem into a linear combination of independent-particle solutions with external auxiliary fields. The phase/sign problem is handled approximately by the phaseless formalism using a trial wave function, which in our calculations was chosen to be the Hartree-Fock solution. We used the consistent correlated basis sets of Peterson and coworkers, which employ a small core relativistic pseudopotential. The AF QMC results are compared with experiment and with those from density-functional (GGA and B3LYP) and coupled-cluster CCSD(T) calculations. The AF QMC total energies agree with CCSD(T) to within a few milli-hartrees across the systems and over several basis sets. The calculated atomic electron affinities, ionization energies, and spectroscopic properties of dimers are, at large basis sets, in excellent agreement with experiment.Comment: 10 pages, 2 figures. To be published in Journal of Chemical Physic

Fixed-node diffusion Monte Carlo study of the structures of m-benzyne

Diffusion Monte Carlo (DMC) calculations are performed on the monocyclic and bicyclic forms of m-benzyne, which are the equilibrium structures at the CCSD(T) and CCSD levels of coupled cluster theory. We employed multi-configuration self-consistent field trial wave functions which are constructed from a carefully selected 8-electrons-in-8-orbitals complete active space [CAS(8,8)], with CSF coefficients that are reoptimized in the presence of a Jastrow factor. The DMC calculations show that the monocyclic structure is lower in energy than the bicyclic structure by 1.9(2) kcal/mole, in excellent agreement with the best coupled cluster results.Comment: 5 pages, 2 figures. to be published in JC

Bond breaking with auxiliary-field quantum Monte Carlo

Bond stretching mimics different levels of electron correlation and provides a challenging testbed for approximate many-body computational methods. Using the recently developed phaseless auxiliary-field quantum Monte Carlo (AF QMC) method, we examine bond stretching in the well-studied molecules BH and N$_2$, and in the H$_{50}$ chain. To control the sign/phase problem, the phaseless AF QMC method constrains the paths in the auxiliary-field path integrals with an approximate phase condition that depends on a trial wave function. With single Slater determinants from unrestricted Hartree-Fock (UHF) as trial wave function, the phaseless AF QMC method generally gives better overall accuracy and a more uniform behavior than the coupled cluster CCSD(T) method in mapping the potential-energy curve. In both BH and N$_2$, we also study the use of multiple-determinant trial wave functions from multi-configuration self-consistent-field (MCSCF) calculations. The increase in computational cost versus the gain in statistical and systematic accuracy are examined. With such trial wave functions, excellent results are obtained across the entire region between equilibrium and the dissociation limit.Comment: 8 pages, 3 figures and 3 tables. Submitted to JC

Eliminating spin contamination in auxiliary-field quantum Monte Carlo: realistic potential energy curve of F2

The use of an approximate reference state wave function |Phi_r> in electronic many-body methods can break the spin symmetry of Born-Oppenheimer spin-independent Hamiltonians. This can result in significant errors, especially when bonds are stretched or broken. A simple spin-projection method is introduced for auxiliary-field quantum Monte Carlo (AFQMC) calculations, which yields spin-contamination-free results, even with a spin-contaminated |Phi_r>. The method is applied to the difficult F2 molecule, which is unbound within unrestricted Hartree-Fock (UHF). With a UHF |Phi_r>, spin contamination causes large systematic errors and long equilibration times in AFQMC in the intermediate, bond-breaking region. The spin-projection method eliminates these problems, and delivers an accurate potential energy curve from equilibrium to the dissociation limit using the UHF |Phi_r>. Realistic potential energy curves are obtained with a cc-pVQZ basis. The calculated spectroscopic constants are in excellent agreement with experiment.Comment: 8 pages, 6 figures, submitted to J. Chem. Phy

Auxiliary-field quantum Monte Carlo calculations of molecular systems with a Gaussian basis

We extend the recently introduced phaseless auxiliary-field quantum Monte Carlo (QMC) approach to any single-particle basis, and apply it to molecular systems with Gaussian basis sets. QMC methods in general scale favorably with system size, as a low power. A QMC approach with auxiliary fields in principle allows an exact solution of the Schrodinger equation in the chosen basis. However, the well-known sign/phase problem causes the statistical noise to increase exponentially. The phaseless method controls this problem by constraining the paths in the auxiliary-field path integrals with an approximate phase condition that depends on a trial wave function. In the present calculations, the trial wave function is a single Slater determinant from a Hartree-Fock calculation. The calculated all-electron total energies show typical systematic errors of no more than a few milli-Hartrees compared to exact results. At equilibrium geometries in the molecules we studied, this accuracy is roughly comparable to that of coupled-cluster with single and double excitations and with non-iterative triples, CCSD(T). For stretched bonds in H$_2$O, our method exhibits better overall accuracy and a more uniform behavior than CCSD(T).Comment: 11 pages, 5 figures. submitted to JC

BEARING CAPACITY OF SQUARE FOOTING ON GEOGRID-REINFORCED LOOSE SAND TO RESIST ECCENTRIC LOAD

This research presents and discuss the results of experimental investigation carried out on geogrids model to study the behavior of geogrid in the loose sandy soil. The effect of location eccentricity, depth of first layer of reinforcement, vertical spacing, number and type of reinforcement layers have been investigated. The results indicated that the percentage of bearing improvement a bout (22 %) at number of reinforced layers N=1 and about (47.5%) at number of reinforced layers N=2 for different Eccentricity values when depth ratio and vertical spacing between layers are (0.5B and 0.75B) respectively

Several small Josephson junctions in a Resonant Cavity: Deviation from the Dicke Model

We have studied quantum-mechanically a system of several small identical Josephson junctions in a lossless single-mode cavity for different initial states, under conditions such that the system is at resonance. This system is analogous to a collection of identical atoms in a cavity, which is described under appropriate conditions by the Dicke model. We find that our system can be well approximated by a reduced Hamiltonian consisting of two levels per junction. The reduced Hamiltonian is similar to the Dicke Hamiltonian, but contains an additional term resembling a dipole-dipole interaction between the junctions. This extra term arises when states outside the degenerate group are included via degenerate second-order (L\"{o}wdin) perturbation theory. As in the Dicke model, we find that, when N junctions are present in the cavity, the oscillation frequency due to the junction-cavity interaction is enhanced by $\sqrt{N}$. The corresponding decrease in the Rabi oscillation period may cause it to be smaller than the decoherence time due to dissipation, making these oscillations observable. Finally, we find that the frequency enhancement survives even if the junctions differ slightly from one another, as expected in a realistic system.Comment: 11 pages. To be published in Phys. Rev.