arXiv subjects

Wenhui Mi

Publications and source records attributed to Wenhui Mi.

At least 19 recordsLinked to original sources

arXiv2026

Systematic study of one-point kinetic energy density functionals for atomic nuclei

To explore the applicability of orbital-free density functional theory (OF-DFT) in nuclear physics, we perform a systematic benchmark of 36 one-point kinetic energy density functionals, which are originally developed for electron systems in condensed matter physics. It is found that the direct use of the original parameters for electron systems leads to inconsistent performance, with certain functionals exhibiting physically unacceptable asymptotic behaviors. However, through parameter re-optimization targeting nuclear densities, different mathematical forms of generalized gradient approximation (GGA) functionals converge to a consistent root-mean-square error of approximately 13 MeV. From a physical perspective, this consistent behavior signifies that the optimized semi-local GGAs have successfully captured the macroscopic, liquid-drop-like background of the nucleus, while the residual deviations appear as periodic oscillations at the magic numbers that could reflect the quantum shell effects.

nucl-th↗

arXiv2026

Unlocking the Power of Orbital-Free Density Functional Theory to Explore the Electronic Structure Under Extreme Conditions

Recent advances in X-ray free-electron laser diagnostics have enabled direct probing of the electronic structure under extreme pressures and temperatures, such as those encountered in stellar interiors and inertial confinement fusion experiments, challenging theoretical models for interpreting experimental data. Kohn-Sham density functional theory (KSDFT) has been successfully applied to analyze experimental X-ray scattering measurements, but its high computational cost renders routine application impractical. Orbital-free DFT (OFDFT) is a substantially more efficient alternative, with computational cost scaling linearly with system size and a weak temperature dependence, yet it often lacks the accuracy required for electronic structure description. Overcoming this limitation, we present a non-empirical Kohn-Sham-assisted orbital-free density functional framework for calculations at extreme conditions, which enables efficient OFDFT simulations with KSDFT-level accuracy for electron densities, electron-ion structure factors, and equations of state across a broad range of conditions. Benchmark comparisons with quantum Monte Carlo data for dense hydrogen and validation against Rayleigh weight measurements of hot dense beryllium demonstrate the reliability of the framework and speedups of up to several hundred times compared with KSDFT. We further show that even at temperatures on the order of 100 eV, quantum non-locality remains essential for correctly describing the electronic structure of dense hydrogen.

cond-mat.mtrl-sci↗

arXiv2025

Ab initio density functional theory approach to warm dense hydrogen: from density response to electronic correlations

Understanding the properties of warm dense hydrogen is of key importance for the modeling of compact astrophysical objects and to understand and further optimize inertial confinement fusion (ICF) applications. The work horse of warm dense matter theory is given by thermal density functional theory (DFT), which, however, suffers from two limitations: (i) its accuracy can depend on the utilized exchange--correlation (XC) functional, which has to be approximated and (ii) it is generally limited to single-electron properties such as the density distribution. Here, we present a new ansatz combining time-dependent DFT results for the dynamic structure factor $S_{ee}(\mathbf{q},\omega)$ with static DFT results for the density response. This allows us to estimate the electron--electron static structure factor $S_{ee}(\mathbf{q})$ of warm dense hydrogen with high accuracy over a broad range of densities and temperatures. In addition to its value for the study of warm dense matter, our work opens up new avenues for the future study of electronic correlations exclusively within the framework of DFT for a host of applications.

physics.plasm-ph↗

arXiv2025

Bridging Theory and Experiment in Materials Discovery: Machine-Learning-Assisted Prediction of Synthesizable Structures

Even though thermodynamic energy-based crystal structure prediction (CSP) has revolutionized materials discovery, the energy-driven CSP approaches often struggle to identify experimentally realizable metastable materials synthesized through kinetically controlled pathways, creating a critical gap between theoretical predictions and experimental synthesis. Here, we propose a synthesizability-driven CSP framework that integrates symmetry-guided structure derivation with a Wyckoff encode-based machine-learning model, allowing for the efficient localization of subspaces likely to yield highly synthesizable structures. Within the identified promising subspaces, a structure-based synthesizability evaluation model, fine-tuned using recently synthesized structures to enhance predictive accuracy, is employed in conjunction with ab initio calculations to systematically identify synthesizable candidates. The framework successfully reproduces 13 experimentally known XSe (X = Sc, Ti, Mn, Fe, Ni, Cu, Zn) structures, demonstrating its effectiveness in predicting synthesizable structures. Notably, 92,310 structures are filtered from the 554,054 candidates predicted by GNoME, exhibiting great potential for promising synthesizability. Additionally, eight thermodynamically favorable Hf-X-O (X = Ti, V, and Mn) structures have been identified, among which three HfV$_2$O$_7$ candidates exhibit high synthesizability, presenting viable candidates for experimental realization and potentially associated with experimentally observed temperature-induced phase transitions. This work establishes a data-driven paradigm for machine-learning-assisted inorganic materials synthesis, highlighting its potential to bridge the gap between computational predictions and experimental realization while unlocking new opportunities for the targeted discovery of novel functional materials.

cond-mat.mtrl-sci↗

arXiv2024

Fast and stable tight-binding framework for nonlocal kinetic energy density functional reconstruction in orbital-free density functional calculations

Nonlocal kinetic energy density functionals (KEDFs) with density-dependent kernels are currently the most accurate functionals available for orbital-free density functional theory (OF-DFT) calculations. However, despite advances in numerical techniques and using only (semi)local density-dependent kernels, nonlocal KEDFs still present substantial computational costs in OF-DFT, limiting their application in large-scale material simulations. To address this challenge, we propose an efficient framework for reconstructing nonlocal KEDFs by incorporating the density functional tight-binding approach, in which the energy functionals are simplified through a first-order functional expansion based on the superposition of free-atom electron densities. This strategy allows the computationally expensive nonlocal kinetic energy and potential calculations to be performed only once during the electron density optimization process, significantly reducing computational overhead while maintaining high accuracy. Benchmark tests using advanced nonlocal KEDFs, such as revHC and LDAK-MGPA, on standard structures including Li, Mg, Al, Ga, Si, III-V semiconductors, as well as Mg$_{50}$ and Si$_{50}$ clusters, demonstrate that our method achieves orders-of-magnitude improvements in efficiency, providing a cost-effective balance between accuracy and computational speed. Additionally, the reconstructed functionals exhibit improved numerical stability for both bulk and finite systems, paving the way for developing more sophisticated KEDFs for realistic material simulations using OF-DFT.

cond-mat.mtrl-sci↗

arXiv2024

Nonlocal free-energy density functional for warm dense matter

Finite-temperature orbital-free density functional theory (FT-OFDFT) holds significant promise for simulating warm dense matter due to its favorable scaling with both system size and temperature. However, the lack of the numerically accurate and transferable noninteracting free energy functionals results in a limit on the application of FT-OFDFT for warm dense matter simulations. Here, a nonlocal free energy functional, named XWMF, was derived by line integrals for FT-OFDFT simulations. Particularly, a designed integral path, wherein the electronic density varies from uniform to inhomogeneous, was employed to accurately describe deviations in response behavior from the uniform electron gas. The XWMF has been benchmarked by a range of warm dense matter systems including the Si, Al, H, He, and H-He mixture. The simulated results demonstrate that FT-OFDFT within XWMF achieves remarkable performance for accuracy and numerical stability. It is worth noting that XWMF exhibits a low computational cost for large-scale ab~initio simulations, offering exciting opportunities for the realistic simulations of warm dense matter systems covering a broad range of temperatures and pressures.

physics.comp-ph↗

arXiv2022

Nonlocal Pseudopotential Energy Density Functional for Orbital-Free Density Functional Theory

Orbital-free density functional theory (OF-DFT) runs at low computational cost that scales linearly with the number of simulated atoms, making it suitable for large-scale material simulations. It is generally considered that OF-DFT strictly requires the use of local pseudopotentials, rather than orbital-dependent nonlocal pseudopotentials, for the calculation of electron-ion interaction energies, as no orbitals are available. This is unfortunate situation since the nonlocal pseudopotentials are known to give much better transferability and calculation accuracy than local ones. We report here the development of a theoretical scheme that allows the direct use of nonlocal pseudopotentials in OF-DFT. In this scheme, a nonlocal pseudopotential energy density functional is derived by the projection of nonlocal pseudopotential onto the non-interacting density matrix (instead of 'orbitals') that can be approximated explicitly as a functional of electron density. Our development defies the belief that nonlocal pseudopotentials are not applicable to OF-DFT, leading to the creation of an alternate theoretical framework of OF-DFT that works superior to the traditional one.

cond-mat.mtrl-sci↗

arXiv2021

GGA-Level Subsystem DFT Achieves Sub-kcal/mol Accuracy Intermolecular Interactions by Mimicking Nonlocal Functionals

The key feature of nonlocal kinetic energy functionals is their ability to reduce to the Thomas-Fermi functional in the regions of high density and to the von Weizsäcker functional in the region of low density/high density gradient. This behavior is crucial when these functionals are employed in subsystem DFT simulations to approximate the nonadditive kinetic energy. We propose a GGA nonadditive kinetic energy functional which mimics the good behavior of nonlocal functionals retaining the computational complexity of typical semilocal functionals. The new functional reproduces Kohn-Sham DFT and benchmark CCSD(T) interaction energies of weakly interacting dimers in the S22-5 and S66 test sets with a mean absolute deviation well below 1 kcal/mol.

cond-mat.mtrl-sci↗

arXiv2021

eQE 2.0: Subsystem DFT Beyond GGA Functionals

By adopting a divide-and-conquer strategy, subsystem-DFT (sDFT) can dramatically reduce the computational cost of large-scale electronic structure calculations. The key ingredients of sDFT are the nonadditive kinetic energy and exchange-correlation functionals which dominate it's accuracy. Even though, semilocal nonadditive functionals find a broad range of applications, their accuracy is somewhat limited especially for those systems where achieving balance between exchange-correlation interactions on one side and nonadditive kinetic energy on the other is crucial. In eQE 2.0, we improve dramatically the accuracy of sDFT simulations by (1) implementing nonlocal nonadditive kinetic energy functionals based on the LMGP family of functionals; (2) adapting Quantum ESPRESSO's implementation of rVV10 and vdW-DF nonlocal exchange-correlation functionals to be employed in sDFT simulations; (3) implementing "deorbitalized" meta GGA functionals (e.g., SCAN-L). We carefully assess the performance of the newly implemented tools on the S22-5 test set. eQE 2.0 delivers excellent interaction energies compared to conventional Kohn-Sham DFT and CCSD(T). The improved performance does not come at a loss of computational efficiency. We show that eQE 2.0 with nonlocal nonadditive functionals retains the same linear scaling behavior achieved in eQE 1.0 with semilocal nonadditive functionals.

cond-mat.mtrl-sci↗

arXiv2020

An Efficient DFT Solver for Nanoscale Simulations and Beyond

We present the One-orbital Ensemble Self-Consistent Field (OE-SCF) method, an {alternative} orbital-free DFT solver that extends the applicability of DFT to system sizes beyond the nanoscale while retaining the accuracy required to be predictive. OE-SCF is an iterative solver where the (typically computationally expensive) Pauli potential is treated as an external potential and updated after each iteration. Because only up to a dozen iterations are needed to reach convergence, OE-SCF dramatically outperforms current orbital-free DFT solvers. Employing merely a single CPU, we carried out the largest ab initio simulation for silicon-based materials to date. OE-SCF is able to converge the energy of bulk-cut Si nanoparticles as a function of their diameter up to 16 nm, for the first time reproducing known empirical results. We model polarization and interface charge transfer when a Si slab is sandwiched between two metal slabs where lattice matching mandates a very large slab size. Additionally, OE-SCF opens the door to adopt even more accurate functionals in orbital-free DFT simulations while still tackling systems sizes beyond the nanoscale.

cond-mat.mtrl-sci↗

arXiv2020

DFTpy: An efficient and object-oriented platform for orbital-free DFT simulations

In silico materials design is hampered by the computational complexity of Kohn-Sham DFT, which scales cubically with the system size. Owing to the development of new-generation kinetic energy density functionals (KEDFs), orbital-free DFT (OFDFT, a linear-scaling method) can now be successfully applied to a large class of semiconductors and such finite systems as quantum dots and metal clusters. In this work, we present DFTpy, an open source software implementing OFDFT written entirely in Python 3 and outsourcing the computationally expensive operations to third-party modules, such as NumPy and SciPy. When fast simulations are in order, DFTpy exploits the fast Fourier transforms (FFTs) from PyFFTW. New-generation, nonlocal and density-dependent-kernel KEDFs are made computationally efficient by employing linear splines and other methods for fast kernel builds. We showcase DFTpy by solving for the electronic structure of a million-atom system of aluminum metal which was computed on a single CPU. The Python 3 implementation is object-oriented, opening the door to easy implementation of new features. As an example, we present a time-dependent OFDFT implementation (hydrodynamic DFT) which we use to compute the spectra of small metal cluster recovering qualitatively the time-dependent Kohn-Sham DFT result. The Python code base allows for easy implementation of APIs. We showcase the combination of DFTpy and ASE for molecular dynamics simulations (NVT) of liquid metals. DFTpy is released under the MIT license.

physics.comp-ph↗

arXiv2019

Nonlocal Subsystem Density Functional Theory

By invoking a divide-and-conquer strategy, subsystem DFT dramatically reduces the computational cost of large-scale, \textit{ab-initio} electronic structure simulations of molecules and materials. The central ingredient setting subsystem DFT apart from Kohn-Sham DFT is the non-additive kinetic energy functional (NAKE). Currently employed NAKEs are at most semilocal (i.e., they only depend on the electron density and its gradient), and as a result of this approximation, so far only systems composed of weakly interacting subsystems have been successfully tackled. In this work, we advance the state-of-the-art by introducing fully nonlocal NAKEs in subsystem DFT simulations for the first time. A benchmark analysis based on the S22-5 test set shows that nonlocal NAKEs considerably improve the computed interaction energies and electron density compared to commonly employed GGA NAKEs, especially when the inter-subsystem electron density overlap is high. Most importantly, we resolve the long standing problem of too attractive interaction energy curves typically resulting from the use of GGA NAKEs.

cond-mat.mtrl-sci↗

arXiv2019

Ab-initio structure and dynamics of supercritical CO2

Green technologies rely on green solvents and fluids. Among them, supercritical CO2 already finds many important applications. The molecular level understanding of the dynamics and structure of this supercritical fluid is a prerequisite to rational design of future green technologies. Unfortunately, the commonly employed Kohn-Sham DFT is too computationally demanding to produce meaningfully converged dynamics within a reasonable time and with a reasonable computational effort. Thanks to subsystem DFT, we analyze finite-size effects by considering simulations cells of varying sizes (up to 256 independent molecules in the cell) and finite-time effects by running 100 ps-long trajectories. We find that the simulations are in reasonable and semiquantitative agreement with the available neutron diffraction experiments and that, as opposed to the gas phase, the CO2 molecules in the fluid are bent with an average OCO angle of 175.8 degrees. Our simulations also confirm that the dimer T-shape is the most prevalent configuration. Our results further strengthen the experiment-simulation agreement for this fluid when comparing radial distribution functions and diffusion coefficient, confirming subsystem DFT as a viable tool for modeling structure and dynamics of condensed-phase systems.

physics.chem-ph↗

arXiv2018

Orbital-Free DFT Correctly Models Quantum Dots When Asymptotics, Nonlocality and Nonhomogeneity Are Accounted For

Million-atom quantum simulations are in principle feasible with Orbital-Free Density Functional Theory (OF-DFT) because the algorithms only require simple functional minimizations with respect to the electron density function. In this context, OF-DFT has been useful for simulations of warm dense matter, plasma, cold metals and alloys. Unfortunately, systems as important as quantum dots and clusters (having highly inhomogeneous electron densities) still fall outside OF-DFT's range of applicability. In this work, we address this century old problem by devising and implementing an accurate, transferable and universal family of nonlocal Kinetic Energy density functionals that feature correct asymptotics and can handle highly inhomogenous electron densities. For the first time to date, we show that OF-DFT achieves close to chemical accuracy for the electronic energy and reproduces the electron density to about 5\% of the benchmark for semiconductor quantum dots and metal clusters. Therefore, this work demonstrates that OF-DFT is no longer limited to simulations of systems with nearly homogeneous electron density but it can venture into simulations of clusters and quantum dots with applicability to rational design of novel materials.

cond-mat.mtrl-sci↗

arXiv2018

Nonlocal Kinetic Energy Functionals By Functional Integration

Since the seminal works of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting Kinetic Energy, $T_s[ρ]$, the subject of this work. The typical paradigm is to first approximate the energy functional, and then take its functional derivative, $\frac{δT_s[ρ]}{δρ(r)}$, yielding a potential that can be used in orbital-free DFT, or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for $T_s[ρ]$ is prescribed (which we dub MGP) having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential derives from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (BCC, FCC) and semiconducting (CD) phases of Silicon as well as of III-V semiconductors. MGP functional is found to be numerically stable typically reaching selfconsistency within 12 iteration of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter (WT) nonlocal functional or any GGA functional.

cond-mat.mtrl-sci↗

arXiv2017

ELSI: A Unified Software Interface for Kohn-Sham Electronic Structure Solvers

Solving the electronic structure from a generalized or standard eigenproblem is often the bottleneck in large scale calculations based on Kohn-Sham density-functional theory. This problem must be addressed by essentially all current electronic structure codes, based on similar matrix expressions, and by high-performance computation. We here present a unified software interface, ELSI, to access different strategies that address the Kohn-Sham eigenvalue problem. Currently supported algorithms include the dense generalized eigensolver library ELPA, the orbital minimization method implemented in libOMM, and the pole expansion and selected inversion (PEXSI) approach with lower computational complexity for semilocal density functionals. The ELSI interface aims to simplify the implementation and optimal use of the different strategies, by offering (a) a unified software framework designed for the electronic structure solvers in Kohn-Sham density-functional theory; (b) reasonable default parameters for a chosen solver; (c) automatic conversion between input and internal working matrix formats, and in the future (d) recommendation of the optimal solver depending on the specific problem. Comparative benchmarks are shown for system sizes up to 11,520 atoms (172,800 basis functions) on distributed memory supercomputing architectures.

physics.comp-ph↗

arXiv2016

A linear scaling method to evaluate the ion-electron potential of crystalline solids

We propose a simple linear scaling expression in reciprocal space for evaluating the ion--electron potential of crystalline solids. The expression replaces the long-range ion--electron potential with an equivalent localized charge distribution and corresponding boundary conditions on the unit cell. Given that no quadratic scaling structure factor is required---as used in traditional methods---the expression shows inherent linear behavior, and is well suited to simulating large-scale systems within orbital-free density functional theory. The scheme is implemented in the ATLAS software package and benchmarked by using a solid Mg bcc lattice containing tens of thousands of atoms in the unit cell. The test results show that the method can efficiently model large crystals with high computational accuracy.

cond-mat.mtrl-sci↗

arXiv2015

ATLAS: A Real-Space Finite-Difference Implementation of Orbital-Free Density Functional Theory

Orbital-free density functional theory (OF-DFT) is a promising method for large-scale quantum mechanics simulation as it provides a good balance of accuracy and computational cost. Its applicability to large-scale simulations has been aided by progress in constructing kinetic energy functionals and local pseudopotentials. However, the widespread adoption of OF-DFT requires further improvement in its efficiency and robustly implemented software. Here we develop a real-space finite-difference method for the numerical solution of OF-DFT in periodic systems. Instead of the traditional self-consistent method, a powerful scheme for energy minimization is introduced to solve the Euler--Lagrange equation. Our approach engages both the real-space finite-difference method and a direct energy-minimization scheme for the OF-DFT calculations. The method is coded into the ATLAS software package and benchmarked using periodic systems of solid Mg, Al, and Al$_{3}$Mg. The test results show that our implementation can achieve high accuracy, efficiency, and numerical stability for large-scale simulations.

physics.comp-ph↗