We present a systematic and comprehensive study of finite-size effects in diffusion quantum Monte Carlo calculations of metals. Several previously introduced schemes for correcting finite-size errors are compared for accuracy and efficiency and pract
ical improvements are introduced. In particular, we test a simple but efficient method of finite-size correction based on an accurate combination of twist averaging and density functional theory. Our diffusion quantum Monte Carlo results for lithium and aluminum, as examples of metallic systems, demonstrate excellent agreement between all of the approaches considered.
We study the potential energy surface of the ozone molecule by means of Quantum Monte Carlo simulations based on the resonating valence bond concept. The trial wave function consists of an antisymmetrized geminal power arranged in a single-determinan
t that is multiplied by a Jastrow correlation factor. Whereas the determinantal part incorporates static correlation effects, the augmented real-space correlation factor accounts for the dynamics electron correlation. The accuracy of this approach is demonstrated by computing the potential energy surface for the ozone molecule in three vibrational states: symmetric, asymmetric and scissoring. We find that the employed wave function provides a detailed description of rather strongly-correlated multi-reference systems, which is in quantitative agreement with experiment.
A theoretical study is reported of the molecular-to-atomic transition in solid hydrogen at high pressure. We use the diffusion quantum Monte Carlo method to calculate the static lattice energies of the competing phases and a density-functional-theory
-based vibrational self-consistent field method to calculate anharmonic vibrational properties. We find a small but significant contribution to the vibrational energy from anharmonicity. A transition from the molecular Cmca-12 direct to the atomic I4_1/amd phase is found at 374 GPa. The vibrational contribution lowers the transition pressure by 91 GPa. The dissociation pressure is not very sensitive to the isotopic composition. Our results suggest that quantum melting occurs at finite temperature.
We present theoretical calculations of the Raman and IR spectra, as well as electronic properties at zero and finite temperature to elucidate the crystal structure of phase III of solid molecular hydrogen. We find that anharmonic finite temperature a
re particularly important and qualitatively influences the main conclusions. While P6$_3$/m is the most likely candidate for phase III at the nuclear ground state, at finite temperature the C2/c structure appears to be more suitable.
Being the simplest element with just one electron and proton the electronic structure of the Hydrogen atom is known exactly. However, this does not hold for the complex interplay between them in a solid and in particular not at high pressure that is
known to alter the crystal as well as the electronic structure. Back in 1935 Wigner and Huntington predicted that at very high pressure solid molecular hydrogen would dissociate and form an atomic solid that is metallic. In spite of intense research efforts the experimental realization, as well as the theoretical determination of the crystal structure has remained elusive. Here we present a computational study showing that the distorted hexagonal P6$_3$/m structure is the most likely candidate for Phase III of solid hydrogen. We find that the pairing structure is very persistent and insulating over the whole pressure range, which suggests that metallization due to dissociation may precede eventual bandgap closure. Due to the fact that this not only resolve one of major disagreement between theory and experiment, but also excludes the conjectured existence of phonon-driven superconductivity in solid molecular hydrogen, our results involve a complete revision of the zero-temperature phase diagram of Phase III.
We apply a variational wave function capable of describing qualitatively and quantitatively the so called resonating valence bond in realistic materials, by improving standard ab initio calculations by means of quantum Monte Carlo methods. In this fr
amework we clearly identify the Kekule and Dewar contributions to the chemical bond of the benzene molecule, and we establish the corresponding resonating valence bond energy of these well known structures ($simeq 0.01$eV/atom). We apply this method to unveil the nature of the chemical bond in undoped graphene and show that this picture remains only within a small resonance length of few atomic units.
