arXiv subjects

Vitaly Gorelov

Publications and source records attributed to Vitaly Gorelov.

13 recordsLinked to original sources

arXiv2026

Signature of Short-Range Order in Static Response of the Three-Dimensional Electron Gas

The three-dimensional electron gas is a fundamental model in condensed matter physics and quantum chemistry, and the exchange-correlation energy derived from it serves as the starting point of \textit{ab initio} computations of materials. However, the wave-vector-dependent response, and hence the static local field factor $G(q)$, has remained without accurate ground-state benchmark in the strongly coupled regime for three decades. Using diffusion Monte Carlo, we calculate $G(q)$ and the static density-density response function across the liquid phase and find a pronounced structure in $G(q)$ at intermediate wave vectors, already visible at metallic densities and growing with increasing interaction strength. We identify it as a fingerprint of short-range order by showing that it is required to reproduce the static structure factor. Our parametrization, valid in the entire liquid phase, predicts a low-energy resonant mode inside the particle-hole continuum.

physics.comp-ph↗

arXiv2026

Designing explicit functionals for the charge density in terms of a potential

One of the most powerful strategies to address properties of real many-body systems is to incorporate data obtained for models, for example, to use data of the homogeneous electron gas in order to build the Local Density Approximation for the Kohn-Sham exchange-correlation potential. In the present work, we examine to what extent we can use model data to design functionals directly for observables of materials. In particular, we study different approximations for the charge density of real inhomogeneous materials expressed as a simple, explicit functional of a given Kohn-Sham potential, using as central building block the Lindhard density-density response function of the homogeneous electron gas. Our increasingly realistic set of approximations includes a fully nearsighted expression equivalent to the Thomas-Fermi approximation, functional Taylor expansions, and different approximations to the Connector Theory developed in [Aouina \textit{et al.}, npj Computational Materials {\bf 11}, 242 (2025)]. In all cases, the charge density is obtained without ever solving the Kohn-Sham Schrödinger equation. Results for cubic helium, a prototypical strongly inhomogeneous material, as well as the covalent semiconductor silicon and metallic aluminum, systematically improve with higher levels of approximation. At the present stage, the results may be used for qualitative discussions or as optimized starting point for a self-consistent Kohn-Sham cycle. More generally, their quality indicates that this is a promising route to obtain functional expressions for observables that are relatively simple to calculate and to analyze.

cond-mat.mtrl-sci↗

arXiv2026

Unbiased Diffusion Monte Carlo for non local operators

We propose a new mathematically exact method for computing unbiased Diffusion Monte Carlo (DMC) estimates of non-local operators. We demonstrate that the current state-of- the-art technique, Forward Walking, is only exact for local quantities and fails to yield unbiased results for the non-local components of reduced density matrices (RDMs). Our method significantly outperforms Forward Walking, as shown in two systems: in the symmetric Hubbard dimer it yields a pure 1RDM; while in the Helium atom it will give an unbiased 1RDM in the limits of zero time step and infinite walkers.

cond-mat.mtrl-sci↗

arXiv2025

Electron charge dynamics and charge separation: A response theory approach

This study applies response theory to investigate electron charge dynamics, with a particular focus on charge separation. We analytically assess the strengths and limitations of linear and quadratic response theories in describing charge density and current, illustrated by a model that simulates charge transfer systems. While linear response accurately captures optical properties, the quadratic response contains the minimal ingredients required to describe charge dynamics and separation. Notably, it closely matches exact time propagation results in some regime that we identify. We propose and test several approximations to the quadratic response and explore the influence of higher-order terms and the effect of an on-site interaction $U$.

cond-mat.mtrl-sci↗

arXiv2024

Electronic excitation spectra of molecular hydrogen in Phase I from Quantum Monte Carlo and Many-Body perturbation methods

We study the electronic excitation spectra in solid molecular hydrogen (phase I) at ambient temperature and 5-90 GPa pressures using Quantum Monte Carlo methods and Many-Body Perturbation Theory. In this range, the system changes from a wide gap molecular insulator to a semiconductor, altering the nature of the excitations from localized to delocalized. Computed gaps and spectra agree with experiments, proving the ability to predict accurately band gaps of many-body systems in presence of nuclear quantum and thermal effects.

cond-mat.mtrl-sci↗

arXiv2023

Exciton band structure of V$_2$O$_5$

Excitonic effects due to the correlation of electrons and holes in excited states of matter dominate the optical spectra of many interesting materials. They are usually studied in the long-wavelength limit. Here we investigate excitons at non-vanishing momentum transfer, corresponding to shorter wavelengths. We calculate the exciton dispersion in the prototypical layered oxide V$_2$O$_5$ by solving the Bethe-Salpeter equation of many-body perturbation theory. We discuss the change of excitation energy and intensity as a function of wavevector for bright and dark excitons, respectively, and we analyze the origin of the excitons along their dispersion. We highlight the important role of the electron-hole exchange with its impact on the exciton dispersion, the singlet-triplet splitting and the difference between the imaginary part of the macroscopic dielectric function and the loss function.

cond-mat.mtrl-sci↗

arXiv2023

Robustness of electronic screening effects in electron spectroscopies: example of V$_2$O$_5$

In bulk and low-dimensional extended systems, the screening of excitations by the electron cloud is a key feature governing spectroscopic properties. Widely used computational approaches, especially in the framework of many-body perturbation theory, such as the GW approximation and the resulting approximate Bethe-Salpeter equation, are explicitly formulated in terms of the screened Coulomb interaction. In the present work we explore the effect of screening in absorption and electron energy loss spectroscopy, concentrating on the effect of local distortions on the screening and elucidating the resulting changes in the various spectra. Using the layered bulk oxide V$_2$O$_5$ as prototype material, we show in which way local distortions affect the screening, and in which way changes in the screening impact electron energy loss and absorption spectra including excitons. We highlight cancellations that make many-body effects in the spectra very robust with respect to structural modifications, while the band structure undergoes significant changes and the nature of the excitations may also be affected. This yields insight concerning the structure-properties relations that are crucial for the use of V$_2$O$_5$ as energy storage material, and more generally, that may be used to optimize the analysis and the calculation of electronic spectra in complex materials.

cond-mat.mtrl-sci↗

arXiv2022

Delocalization of dark and bright excitons in flat-band materials and the optical properties of V$_2$O$_5$

The simplest picture of excitons in materials with atomic-like localization of electrons is that of Frenkel excitons, where electrons and holes stay close together, which is associated with a large binding energy. Here, using the example of the layered oxide V$_2$O$_5$ , we show how localized charge-transfer excitations combine to form excitons that also have a huge binding energy but, at the same time, a large electron-hole distance, and we explain this seemingly contradictory finding. The anisotropy of the exciton delocalization is determined by the local anisotropy of the structure, whereas the exciton extends orthogonally to the chains formed by the crystal structure. Moreover, we show that the bright exciton goes together with a dark exciton of even larger binding energy and more pronounced anisotropy. These findings are obtained by combining first principles many-body perturbation theory calculations, ellipsometry experiments, and tight binding modelling, leading to very good agreement and a consistent picture. Our explanation is general and can be extended to other materials.

cond-mat.mtrl-sci↗

arXiv2020

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

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.

cond-mat.mtrl-sci↗

arXiv2020

Electronic energy gap closure and metal-insulator transition in dense liquid hydrogen

Using Quantum Monte Carlo (QMC) calculations, we investigate the insulator-metal transition observed in liquid hydrogen at high pressure. Below the critical temperature of the transition from the molecular to the atomic liquid, the fundamental electronic gap closure occurs abruptly, with a small discontinuity reflecting the weak first-order transition in the thermodynamic equation of state. Above the critical temperature, molecular dissociation sets in while the gap is still open. When the gap closes, the decay of the off-diagonal reduced density matrix shows that the liquid enters a gapless, but localized phase: there is a cross-over between the insulating and the metallic liquids. Compared to different DFT functionals, our QMC calculations provide larger values for the fundamental gap and the electronic density of states close to the band edges, indicating that optical properties from DFT potentially benefit from error cancellations.

cond-mat.mtrl-sci↗

arXiv2020

Energy gap closure of crystalline molecular hydrogen with pressure

We study the gap closure with pressure of crystalline molecular hydrogen. The gaps are obtained from grand-canonical Quantum Monte Carlo methods properly extended to quantum and thermal crystals, simulated by Coupled Electron Ion Monte Carlo. Nuclear zero point effects cause a large reduction in the gap ($\sim 2eV$). \CP{Depending on the structure,} the fundamental indirect gap closes \CP{between 380GPa and} 530GPa for ideal crystals and 330-380GPa for quantum crystals. Beyond this pressure the system enters into a bad metal phase where the density of states at the Fermi level increases with pressure up to $\sim$450\CP{-500} GPa when the direct gap closes. Our work partially supports the interpretation of recent experiments in high pressure hydrogen.

cond-mat.mtrl-sci↗

arXiv2019

Electronic band gaps from Quantum Monte Carlo methods

We develop a method for calculating the fundamental electronic gap of semiconductors and insulators using grand canonical Quantum Monte Carlo simulations. We discuss the origin of the bias introduced by supercell calculations of finite size and show how to correct the leading and subleading finite size errors either based on observables accessible in the finite-sized simulations or from DFT calculations. Our procedure is applied to solid molecular hydrogen and compared to experiment for carbon and silicon crystals.

cond-mat.mtrl-sci↗

arXiv2018

Benchmarking vdW-DF first principle predictions against Coupled Electron-Ion Monte Carlo for high pressure liquid hydrogen

We report first principle results for nuclear structure and optical responses of high pressure liquid hydrogen along two isotherms in the region of molecular dissociation. We employ Density Functional Theory with the vdW-DF approximation (vdW) and we benchmark the results against existing predictions from Coupling Electron-Ion Monte Carlo (CEIMC). At fixed density and temperature, we find that pressure from vdW is higher than pressure from CEIMC by about 10 GPa in the molecular insulating phase and about 20 GPa in the dissociated metallic phase. Molecules are found to be overstabilized using vdW, with a slightly shorter bond length, and with a stronger resistance to compression. As a consequence, pressure dissociation along isotherms using vdW is more progressive than computed with CEIMC. Below the critical point, the liquid-liquid phase transition is observed with both theories in the same density region but the one predicted by vdW has a smaller density discontinuity, i.e. a smaller first order character. The optical conductivity computed using Kubo-Greenwood is rather similar for the two systems and reflects the slightly more pronounced molecular character of vdW.

cond-mat.mtrl-sci↗