Quantum-mechanical interatomic potentials with electron temperature for strong-coupling transition metals.

In narrow d-band transition metals, electron temperature T(el) can impact the underlying electronic structure for temperatures near and above melt, strongly coupling the ion- and electron-thermal degrees of freedom and producing T(el)-dependent interatomic forces. Starting from the Mermin formulation of density functional theory, we have extended first-principles generalized pseudopotential theory to finite electron temperature and then developed efficient T(el)-dependent model generalized pseudopotential theory interatomic potentials for a Mo prototype. Unlike potentials based on the T(el)=0 electronic structure, the T(el)-dependent model generalized pseudopotential theory potentials yield a high-pressure Mo melt curve consistent with density functional theory quantum simulations, as well as with dynamic experiments, and also support a rich polymorphism in the high-(T,P) phase diagram.

Prospects for release-node quantum Monte Carlo.

We perform release-node quantum Monte Carlo simulations on the first row diatomic molecules in order to assess how accurately their ground-state energies can be obtained. An analysis of the fermion-boson energy difference is shown to be strongly dependent on the nuclear charge, Z, which in turn determines the growth of variance of the release-node energy. It is possible to use maximum entropy analysis to extrapolate to ground-state energies only for the low Z elements.

Systematic reduction of sign errors in many-body calculations of atoms and molecules.

The self-healing diffusion Monte Carlo algorithm (SHDMC) is shown to be an accurate and robust method for calculating the ground state of atoms and molecules. By direct comparison with accurate configuration interaction results for the oxygen atom, we show that SHDMC converges systematically towards the ground-state wave function. We present results for the challenging N2 molecule, where the binding energies obtained via both energy minimization and SHDMC are near chemical accuracy (1  kcal/mol).

Neutral and charged excitations in carbon fullerenes from first-principles many-body theories.

We investigate the accuracy of first-principles many-body theories at the nanoscale by comparing the low-energy excitations of the carbon fullerenes C(20), C(24), C(50), C(60), C(70), and C(80) with experiment. Properties are calculated via the GW-Bethe-Salpeter equation and diffusion quantum Monte Carlo methods. We critically compare these theories and assess their accuracy against available photoabsorption and photoelectron spectroscopy data.

Insulator to metal transition in fluid deuterium.

We have investigated the insulator to metal transition in fluid deuterium using first principles simulations. Both density functional and quantum Monte Carlo calculations indicate that the electronic energy gap of the liquid vanishes at about ninefold compression and 3000 K. At these conditions the computed conductivity values are characteristic of a poor metal.

Quantum Monte Carlo study of the optical and diffusive properties of the vacancy defect in diamond.

Fixed-node diffusion quantum Monte Carlo (DMC) calculations of the ground and excited state energetics of the neutral vacancy defect in diamond are reported. The multiplet structure of the defect is modeled using guiding wave functions of the Slater-Jastrow type with symmetrized multideterminant Slater parts. For the ground state we obtain the 1E state in agreement with experiment.

Quantum Monte Carlo calculations of nanostructure optical gaps: application to silicon quantum dots.

Quantum Monte Carlo (QMC) calculations of the optical gaps of silicon quantum dots ranging in size from 0 to 1.5 nm are presented. These QMC results are used to examine the accuracy of density functional (DFT) and empirical pseudopotential based calculations.

Dissociation of water under pressure.

The dissociation of water under pressure is investigated with a series of ab initio molecular dynamics simulations at thermodynamic conditions close to those obtained in shock wave experiments. We find that molecular dissociation occurs via a bimolecular process similar to ambient conditions, leading to the formation of short-lived hydronium ions. Up to twofold compression and 2000 K, the oxygen diffusion coefficient is characteristic of a fluid.

Linear-scaling quantum Monte Carlo calculations.

A method is presented for using truncated, maximally localized Wannier functions to introduce sparsity into the Slater determinant part of the trial wave function in quantum Monte Carlo calculations. When combined with an efficient numerical evaluation of these localized orbitals, the dominant cost in the calculation, namely, the evaluation of the Slater determinant, scales linearly with system size. This technique is applied to accurate total energy calculation of hydrogenated silicon clusters and carbon fullerenes containing 20-1000 valence electrons.