arXiv subjects

W. A. Al-Saidi

Publications and source records attributed to W. A. Al-Saidi.

13 recordsLinked to original sources

arXiv2008

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.

physics.chem-ph↗

arXiv2007

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.

physics.comp-ph↗

arXiv2007

Optimized norm-conserving Hartree-Fock pseudopotentials for plane-wave calculations

We report Hartree-Fock (HF) based pseudopotentials suitable for plane-wave calculations. Unlike typical effective core potentials, the present pseudopotentials are finite at the origin and exhibit rapid convergence in a plane-wave basis; the optimized pseudopotential method [A. M. Rappe et. al, Phys. Rev. B 41 1227--30 (1990)] improves plane-wave convergence. Norm-conserving HF pseudopotentials are found to develop long-range non-Coulombic behavior which does not decay faster than 1/r, and is non-local. This behavior, which stems from the nonlocality of the exchange potential, is remedied using a recently developed self-consistent procedure [J. R. Trail and R. J. Needs, J. Chem. Phys. 122, 014112 (2005)]. The resulting pseudopotentials slightly violate the norm conservation of the core charge. We calculated several atomic properties using these pseudopotentials, and the results are in good agreement with all-electron HF values. The dissociation energies, equilibrium bond lengths, and frequency of vibrations of several dimers obtained with these HF pseudopotentials and plane waves are also in good agreement with all-electron results.

cond-mat.mtrl-sci↗

arXiv2007

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.

physics.comp-ph↗

arXiv2007

A study of H+H$_2$ and several H-bonded molecules by phaseless auxiliary-field quantum Monte Carlo with planewave and Gaussian basis sets

We present phaseless auxiliary-field (AF) quantum Monte Carlo (QMC) calculations of the ground states of some hydrogen-bonded systems. These systems were selected to test and benchmark different aspects of the new phaseless AF QMC method. They include the transition state of H+H$_2$ near the equilibrium geometry and in the van der Walls limit, as well as H$_2$O, OH, and H$_2$O$_2$ molecules. Most of these systems present significant challenges for traditional independent-particle electronic structure approaches, and many also have exact results available. The phaseless AF QMC method is used either with a planewave basis with pseudopotentials or with all-electron Gaussian basis sets. For some systems, calculations are done with both to compare and characterize the performance of AF QMC under different basis sets and different Hubbard-Stratonovich decompositions. Excellent results are obtained using as input single Slater determinant wave functions taken from independent-particle calculations. Comparisons of the Gaussian based AF QMC results with exact full configuration show that the errors from controlling the phase problem with the phaseless approximation are small. At the large basis-size limit, the AF QMC results using both types of basis sets are in good agreement with each other and with experimental values.

physics.comp-ph↗

arXiv2006

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.

physics.comp-ph↗

arXiv2006

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).

physics.comp-ph↗

arXiv2005

Auxiliary-field quantum Monte Carlo study of TiO and MnO molecules

Calculations of the binding energy of the transition metal oxide molecules TiO and MnO are presented, using a recently developed phaseless auxiliary field quantum Monte Carlo approach. This method maps the interacting many-body problem onto a linear combination of non-interacting problems by a complex Hubbard-Stratonovich transformation, and controls the phase/sign problem with a phaseless approximation relying on a trial wave function. It employs random walks in Slater determinant space to project the ground state of the system, and allows use of much of the same machinery as in standard density functional theory calculations, such as planewave basis and non-local pseudopotentials. The calculations used a single Slater determinant trial wave function obtained from a density functional calculation, with no further optimization. The calculated binding energies are in good agreement with experiment and with recent diffusion Monte Carlo results. Together with previous results for sp-bonded systems, the present study indicates that the phaseless auxiliary field method is a robust and promising approach for the study of correlation effects in real materials.

cond-mat.str-el↗

arXiv2003

Quantum Monte Carlo Study of a Disordered 2-D Josephson Junction Array

We have studied the superconducting-insulating phase transition in a disordered two-dimensional Josephson junction array, using quantum Monte Carlo techniques. We consider disorder in both the capacitive energies and in the values of the offset charges. The calculated phase diagram shows that the lobe structure of the phase diagram disappears for sufficiently strong disorder in the offset charge. Our results agree quite well with previous calculations carried out using a mean-field approximation.

cond-mat.supr-con↗

arXiv2003

Langevin vortex dynamics for a layered superconductor in the lowest Landau level approximation

We have numerically investigated the dynamics of vortices in a clean layered superconductor placed in a perpendicular magnetic field. We describe the energetics using a Ginzburg-Landau free energy functional in the lowest Landau level approximation. The dynamics are determined using the time-dependent Ginzburg-Landau approximation, and thermal fluctuations are incorporated via a Langevin term. The c-axis conductivity at nonzero frequencies, as calculated from the Kubo formalism, shows a strong but not divergent increase as the melting temperature $T_M$ is approached from above, followed by an apparently discontinuous drop at the vortex lattice freezing temperature. The discontinuity is consistent with the occurrence of a first-order freezing. The calculated equilibrium properties agree with previous Monte Carlo studies using the same Hamiltonian. We briefly discuss the possibility of detecting this fluctuation conductivity experimentally.

cond-mat.supr-con↗

arXiv2002

Phase phonon spectrum and melting in a quantum rotor model with diagonal disorder

We study the zero-temperature ($T = 0$) quantum rotor model with on-site disorder in the charging energy. Such a model may serve as an idealized Hamiltonian for an array of Josephson-coupled small superconducting grains, or superfluid $^4$He in a disordered environment. In the approximation of small-amplitude phase fluctuations, the Hamiltonian maps onto a system of coupled harmonic oscillators with on-site disorder. We study the effects of disorder in this harmonic regime, using the coherent potential approximation (CPA), obtaining the density of states and the lifetimes of the spin-wave-like excitations for several choices of the parameters which characterize the disorder. Finally, we estimate the parameters characterizing the $T = 0$ quantum melting of the phase order, using a suitable Lindemann criterion.

cond-mat.supr-con↗

arXiv2002

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 (Löwdin) 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.

cond-mat.supr-con↗

arXiv2001

Eigenstates of a Small Josephson Junction Coupled to a Resonant Cavity

We carry out a quantum-mechanical analysis of a small Josephson junction coupled to a single-mode resonant cavity. We find that the eigenstates of the combined junction-cavity system are strongly entangled only when the gate voltage applied at one of the superconducting islands is tuned to certain special values. One such value corresponds to the resonant absorption of a single photon by Cooper pairs in the junction. Another special value corresponds to a {\em two-photon} absorption process. Near the single-photon resonant absorption, the system is accurately described by a simplified model in which only the lowest two levels of the Josephson junction are retained in the Hamiltonian matrix. We noticed that this approximation does not work very well as the number of photons in the resonator increases. Our system shows also the phenomenon of ``collapse and revival'' under suitable initial conditions, and our full numerical solution agrees with the two level approximation result.

cond-mat.supr-con↗