Nonthermal solid-solid phase transition in ferromagnetic iron

We posit the existence of a nonthermal phase transition in iron, driven by a loss of ferromagnetic ordering on ultrafast timescales with increasing electron temperature. The transition corresponds to a solid-solid BCC to FCC phase transformation and takes place at an electron temperature of 0.62 eV while the ion lattice remains near room temperature. The BCC structure initially undergoes phonon softening during the magnetic transformation, followed by a solid-solid phase transition to the FCC structure, and a subsequent hardening of phonon modes. We present a detailed physical picture of the process, supported by finite-temperature density functional theory simulations of the phonon dispersion curves, electronic density of states, and thermodynamic free energy

Correlation energy of the spin-polarized electron liquid studied using quantum Monte Carlo simulations

Variational and diffusion quantum Monte Carlo (VMC and DMC) methods with Slater-Jastrowbackflow trial wave functions are used to study the spin-polarized three-dimensional uniform electron fluid. We report ground state VMC and DMC energies in the density range 0.5 ≤ rs ≤ 20. Finite-size errors are corrected using canonical-ensemble twist-averaged boundary conditions and extrapolation of the twist-averaged energy per particle calculated at three system sizes (N =113, 259, and 387) to the thermodynamic limit of infinite system size. The DMC energies in the thermodynamic limit are used to parameterize a local spin density approximation correlation function for inhomogeneous electron systems

Correlation energy of the spin-polarized electron liquid by quantum Monte Carlo

Variational and diffusion quantum Monte Carlo (VMC and DMC) methods with Slater-Jastrow-backflow trial wave functions are used to study the spin-polarized three-dimensional uniform electron fluid. We report ground state VMC and DMC energies in the density range $0.5 \leq r_\text{s} \leq 20$. Finite-size errors are corrected using canonical-ensemble twist-averaged boundary conditions and extrapolation of the twist-averaged energy per particle calculated at three system sizes (N=113, 259, and 387) to the thermodynamic limit of infinite system size. The DMC energies in the thermodynamic limit are used to parameterize a local spin density approximation correlation function for inhomogeneous electron systems.Comment: arXiv admin note: substantial text overlap with arXiv:2209.1022

Quantifying ionization in hot dense plasmas

Ionization is a problematic quantity in that it does not have a well-defined thermodynamic definition, yet it is a key parameter within plasma modelling. One still therefore aims to find a consistent and unambiguous definition for the ionization state. Within this context we present finite-temperature density functional theory calculations of the ionization state of carbon in CH plasmas using two potential definitions: one based on counting the number of continuum electrons, and another based on the optical conductivity. Differences of up to 10% are observed between the two methods. However, including “Pauli forbidden” transitions in the conductivity reproduces the counting definition, suggesting such transitions are important to evaluate the ionization state

Learning the exchange-correlation functional from nature with fully differentiable density functional theory

Improving the predictive capability of molecular properties in ab initio simulations is essential for advanced material discovery. Despite recent progress making use of machine learning, utilizing deep neural networks to improve quantum chemistry modeling remains severely limited by the scarcity and heterogeneity of appropriate experimental data. Here we show how training a neural network to replace the exchange-correlation functional within a fully differentiable three-dimensional Kohn-Sham density functional theory framework can greatly improve simulation accuracy. Using only eight experimental data points on diatomic molecules, our trained exchange-correlation networks enable improved prediction accuracy of atomization energies across a collection of 104 molecules containing new bonds, and atoms, that are not present in the training dataset

Simulations of Collisional Effects in an Inner-Shell Solid-Density Mg X-Ray Laser

Inner-shell K$\alpha$ x-ray lasers have been created by pumping gaseous, solid, and liquid targets with the intense x-ray output of free-electron-lasers (FELs). For gaseous targets lasing relies on the creation of K-shell core-holes on a time-scale short compared with filling via Auger decay. In the case of solid and liquid density systems, collisional effects will also be important, affecting not only populations, but also line-widths, both of which impact the degree of overall gain, and its duration. However, to date such collisional effects have not been extensively studied. We present here initial simulations using the CCFLY code of inner-shell lasing in solid density Mg, where we self-consistently treat the effects of the incoming FEL radiation and the atomic kinetics of the Mg system, including radiative, Auger, and collisional effects. We find that the combination of collisional population of the lower states of the lasing transitions and broadening of the lines precludes lasing on all but the K$\alpha$ of the initially cold system. Even assuming instantaneous turning on of the FEL pump, we find the duration of the gain in the solid system to be sub-femtosecond.Comment: This paper has been submitted to Philosophical Transactions

Correlation energy of the paramagnetic electron gas at the thermodynamic limit

The variational and diffusion quantum Monte Carlo methods are used to calculate the correlation energy of the paramagnetic three-dimensional homogeneous electron gas at intermediate to high density. Ground state energies in finite cells are determined using Slater-Jastrow-backflow trial wave functions, and finite-size errors are removed using twist-averaged boundary conditions and extrapolation of the energy per particle to the thermodynamic limit of infinite system size. Our correlation energies in the thermodynamic limit are lower (i.e., more negative, and therefore more accurate according to the variational principle) than previous results, and can be used for the parameterization of density functionals to be applied to high-density systems

Quantum Monte Carlo study of the phase diagram of the two-dimensional uniform electron liquid

We present a study of spin-unpolarized and spin-polarized two-dimensional uniform electron liquids using variational and diffusion quantum Monte Carlo (VMC and DMC) methods with Slater-Jastrow-backflow trial wave functions. Ground-state VMC and DMC energies are obtained in the density range $1 \leq r_\text{s} \leq 40$. Single-particle and many-body finite-size errors are corrected using canonical-ensemble twist-averaged boundary conditions and extrapolation of twist-averaged energies to the thermodynamic limit of infinite system size. System-size-dependent errors in Slater-Jastrow-backflow DMC energies caused by partially converged VMC energy minimization calculations are discussed. We find that, for $1 \leq r_\text{s} \leq 5$, optimizing the backflow function at each twist lowers the twist-averaged DMC energy at finite system size. However, nonsystematic system-size-dependent effects remain in the DMC energies, which can be partially removed by extrapolation from multiple finite system sizes to infinite system size. We attribute these nonsystematic effects to the close competition between fluid and defected crystal phases at different system sizes at low density. The DMC energies in the thermodynamic limit are used to parameterize a local spin density approximation correlation functional for inhomogeneous electron systems. Our zero-temperature phase diagram shows a single transition from a paramagnetic fluid to a hexagonal Wigner crystal at $r_\text{s}=35(1)$, with no region of stability for a ferromagnetic fluid

Exploring relaxation dynamics in warm dense plasmas by tailoring non-thermal electron distributions with a free electron laser

Knowing the characteristic relaxation time of free electrons in a dense plasma is crucial to our understanding of plasma equilibration and transport. However, experimental investigations of electron relaxation dynamics have been hindered by the ultra-fast, sub-femtosecond timescales on which these interactions typically take place. Here we propose a novel approach that uses x-rays from a free electron laser to generate well-defined non-thermal electron distributions, which can then be tracked via emission spectroscopy from radiative recombination as they thermalize. Collisional radiative simulations reveal how this method can enable the measurement of electron relaxation timescales in situ, shedding light on the applicability and accuracy of the Coulomb Logarithm framework for modelling collisions in dense plasmas