Periodic Subsystem Density-Functional Theory

Abstract

By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem DFT has recently emerged as a powerful tool for reducing the computational scaling of Kohn--Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extening FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement (but still within chemical accuracy) with Kohn--Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.

References in corpus (7)

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• O(N) methods in electronic structure calculations
• Periodic Subsystem Density-Functional Theory
• A DFT Approach to Non-Covalent Interactions via Monomer Polarization and Pauli Blockade
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Cited by in corpus (8)

• Quantum simulations of materials on near-term quantum computers
• Quantum Embedding Theory for Strongly-correlated States in Materials
• Periodic Subsystem Density-Functional Theory
• Subsystem real-time Time Dependent Density Functional Theory
• First-principles Studies of Strongly Correlated States in Defect Spin Qubits in Diamond
• eQE 2.0: Subsystem DFT Beyond GGA Functionals
• Advances in Quantum Defect Embedding Theory
• GGA-Level Subsystem DFT Achieves Sub-kcal/mol Accuracy Intermolecular Interactions by Mimicking Nonlocal Functionals