Authors: Hsin-Yu Ko | Marcos F. Calegari Andrade | Zachary M. Sparrow | Ju-an Zhang | Robert A. DiStasio
Source: Journal of Chemical Theory and Computation (article, 2023-06-29)
Field: Materials Science — Materials Chemistry

High-Throughput Condensed-Phase Hybrid Density Functional Theory for Large-Scale Finite-Gap Systems: The <tt>SeA</tt> Approach High-throughput electronic structure calculations (often performed using density functional theory (DFT)) play a central role in screening existing and novel materials, sampling potential energy surfaces, and generating data for machine learning applications. By including a fraction of exact exchange (EXX), hybrid functionals reduce the self-interaction error in semilocal DFT and furnish a more accurate description of the underlying electronic structure, albeit at a computational cost that often prohibits such high-throughput applications. To address this challenge, we have constructed a robust, accurate, and computationally efficient framework for high-throughput condensed-phase hybrid DFT and implemented this approach in the PWSCF module of Quantum ESPRESSO (QE). The resulting SeA approach (SeA = SCDM + exx + ACE) combines and seamlessly integrates: (<i>i</i>) the selected columns of the density matrix method (SCDM, a robust noniterative orbital localization scheme that sidesteps system-dependent optimization protocols), (<i>ii</i>) a recently extended version of exx (a black-box linear-scaling EXX algorithm that exploits sparsity between localized orbitals in real space when evaluating the action of the standard/full-rank <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mover><mml:mi>V</mml:mi><mml:mo>^</mml:mo></mml:mover><mml:mi>xx</mml:mi></mml:msub></mml:math> operator), and (<i>iii</i>) adaptively compressed exchange (ACE, a low-rank <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mover><mml:mi>V</mml:mi><mml:mo>^</mml:mo></mml:mover><mml:mi>xx</mml:mi></mml:msub></mml:math> approximation). In doing so, SeA harnesses three levels of computational savings: <i>pair selection</i> and <i>domain truncation</i> from SCDM + exx (which only considers spatially overlapping orbitals on orbital-pair-specific and system-size-independent domains) and <i>low-rank</i> <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mover><mml:mi>V</mml:mi><mml:mo>^</mml:mo></mml:mover><mml:mi>xx</mml:mi></mml:msub></mml:math> <i>approximation</i> from ACE (which reduces the number of calls to SCDM + exx during the self-consistent field (SCF) procedure). Across a diverse set of 200 nonequilibrium (H<sub>2</sub>O)<sub>64</sub> configurations (with densities spanning 0.4-1.7 g/cm<sup>3</sup>), SeA provides a 1-2 order-of-magnitude speedup in the overall time-to-solution, i.e., ≈8-26× compared to the convolution-based PWSCF(ACE) implementation in QE and ≈78-247× compared to the conventional PWSCF(Full) approach, and yields energies, ionic forces, and other properties with high fidelity. As a proof-of-principle high-throughput application, we trained a deep neural network (DNN) potential for ambient liquid water at the hybrid DFT level using SeA via an actively learned data set with ≈8,700 (H<sub>2</sub>O)<sub>64</sub> configurations. Using an out-of-sample set of (H<sub>2</sub>O)<sub>512</sub> configurations (at nonambient conditions), we confirmed the accuracy of this SeA-trained potential and showcased the capabilities of SeA by computing the ground-truth ionic forces in this challenging system containing >1,500 atoms. Density functional theory ; Throughput ; Scale (ratio) ; Phase (matter) ; Computer science ; Statistical physics ; Physics ; Materials science ; Quantum mechanics ; Telecommunications Machine Learning in Materials Science ; Advanced Thermoelectric Materials and Devices ; Inorganic Chemistry and Materials