Electronic structure and optical properties of quantum crystals from first principles calculations in the Born-Oppenheimer approximation

Abstract

We develop a formalism to accurately account for the renormalization of electronic structure due to quantum and thermal nuclear motions within the Born-Oppenheimer approximation. We focus on the fundamental energy gap obtained from electronic addition and removal energies from Quantum Monte Carlo calculations in either the canonical or grand canonical ensembles. The formalism applies as well to effective single electron theories such as those based on Density Functional Theory. We show that electronic (Bloch) crystal momentum can be restored by marginalizing the total electron-ion wave function with respect to the nuclear equilibrium distribution, and we describe an explicit procedure to establish the band structure of electronic excitations for quantum crystals within the Born-Oppenheimer approximation. Based on the Kubo-Greenwood equation, we discuss the effects of nuclear motion on optical conductivity. Our methodology applies to the low temperature regime where nuclear motion is quantized and in general differs from the semi-classical approximation. We apply our method to study the electronic structure of C2/c-24 crystalline hydrogen at 200K and 250 GPa and discuss the optical absorption profile of hydrogen crystal at 200K and carbon diamond at 297K.

References in corpus (47)

• Advanced capabilities for materials modelling with Quantum ESPRESSO
• Electron-phonon interactions from first principles
• Anharmonic free energies and phonon dispersions from the stochastic self-consistent harmonic approximation: application to platinum and palladium hydrides
• i-PI 2.0: A Universal Force Engine for Advanced Molecular Simulations
• Twist-averaged Boundary Conditions in Continuum Quantum Monte Carlo
• Path Integral Monte Carlo Calculation of the Deuterium Hugoniot
• Molecular Dissociation in Hot, Dense Hydrogen
• The Finite Size Error in Many-body Simulations with long-Ranged Interactions
• Finite-size errors in continuum quantum Monte Carlo calculations
• One-shot calculation of temperature-dependent optical spectra and phonon-induced band-gap renormalization
• Applications of quantum Monte Carlo methods in condensed systems
• {\it Ab--initio} finite temperature excitons
• Variational and Diffusion Quantum Monte Carlo Calculations with the CASINO Code
• Stable liquid Hydrogen at high pressure by a novel ab-initio molecular dynamics
• Effect of the quantistic zero-point atomic motion on the opto-electronic properties of diamond and trans-polyacetylene
• The temperature dependence of electronic eigenenergies in the adiabatic harmonic approximation
• Kubo-Greenwood Electrical Conductivity Formulation and Implementation for Projector Augmented Wave Datasets
• Theory of Finite Size Effects for Electronic Quantum Monte Carlo Calculations of Liquids and Solids
• Theory of the special displacement method for electronic structure calculations at finite temperature
• Temperature dependent excitonic effects in the optical properties of single-layer MoS${}_2$
• Quantum Monte Carlo study of the phase diagram of solid molecular hydrogen at extreme pressures
• Quantum Monte Carlo applied to solids
• Coupled Electron Ion Monte Carlo Calculations of Dense Metallic Hydrogen
• Towards a Predictive First-Principles Description of Solid Molecular Hydrogen with Density-Functional Theory
• Momentum Distribution and Renormalization Factor in Sodium and the Electron Gas
• The effect of electron correlation on the electronic structure and spin-lattice coupling of the high-T${}_c$ cuprates: quantum Monte Carlo calculations
• Discovering correlated fermions using quantum Monte Carlo
• TurboRVB: a many-body toolkit for {\it ab initio} electronic simulations by quantum Monte Carlo
• A path-integral molecular dynamics simulation of diamond
• Unified theory of electron-phonon renormalization and phonon-assisted optical absorption
• Electron-electron and electron-phonon correlation effects on the finite temperature electronic and optical properties of zb-GaN
• Fully Anharmonic, Non-Perturbative Theory of Vibronically Renormalized Electronic Band Structures
• Giant electron-phonon interactions in molecular crystals and the importance of non-quadratic coupling
• Quantum Monte Carlo calculations of energy gaps from first principles
• Coupled Electron-Ion Monte Carlo simulation of hydrogen molecular crystals
• Electronic band gaps from Quantum Monte Carlo methods
• Phonon-induced renormalization of electron wave functions
• Energy gap closure of crystalline molecular hydrogen with pressure
• Optical properties of high pressure liquid hydrogen across molecular dissociation
• Temperature effects on the electronic band structure of PbTe from first principles
• Path-integral molecular dynamics simulation of 3C-SiC
• Doping a Bad Metal: Origin of Suppression of Metal-Insulator Transition in Non-Stoichiometric VO${}_2$
• An efficient method for grand-canonical twist averaging in quantum Monte Carlo calculations
• Electronic energy gap closure and metal-insulator transition in dense liquid hydrogen
• Quantum Monte Carlo Compton profiles of solid and liquid lithium
• Ab Initio Electronic Structure Calculations by Auxiliary-Field Quantum Monte Carlo
• Coupled Electron Ion Monte Carlo Calculations of Atomic Hydrogen

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