Enabling Large-Scale Condensed-Phase Hybrid Density Functional Theory Based $Ab$ $Initio$ Molecular Dynamics II: Extensions to the Isobaric-Isoenthalpic and Isobaric-Isothermal Ensembles

TL;DR

This paper extends a linear-scaling hybrid DFT AIMD method to handle large-scale condensed-phase systems with fluctuating cells in various thermodynamic ensembles, improving computational efficiency and scalability.

Contribution

It introduces theoretical and algorithmic extensions to the exx code, enabling hybrid DFT AIMD in NpH/NpT ensembles with general cells and stress tensor evaluation.

Findings

The extended exx evaluates the stress tensor with negligible cost.

It remains highly scalable across different HPC architectures.

The method enables routine hybrid DFT AIMD for large systems under various conditions.

Abstract

In the previous paper of this series [JCTC 2020, 16, 3757], we presented a theoretical and algorithmic framework based on a localized representation of the occupied space that exploits the inherent sparsity in the real-space evaluation of the EXX interaction in finite-gap systems. This was accompanied by a detailed description of exx, a massively parallel hybrid MPI/OpenMP implementation of this approach in Quantum ESPRESSO that enables linear-scaling hybrid DFT based AIMD in the NVE/NVT ensembles of condensed-phase systems containing 500--1000 atoms (in fixed orthorhombic cells) with a wall time cost comparable to semi-local DFT. In this work, we extend exx to enable hybrid DFT based AIMD of large-scale condensed-phase systems with general and fluctuating cells in the NpH/NpT ensembles. Our theoretical extension includes an analytical derivation of the EXX contribution to the stress tensor for systems in general cells with a computational complexity that scales linearly with system size. The corresponding algorithmic extensions to exx include optimized routines that: (i) handle static/fluctuating cells with non-orthogonal lattice symmetries, (ii) solve Poisson's equation in general cells via an automated selection of the auxiliary grid directions in the Natan-Kronik representation of the discrete Laplacian operator, and (iii) evaluate the EXX contribution to the stress tensor. We also critically assess the computational performance of the extended exx module across several different HPC architectures via case studies on ice Ih, II, and III as well as ambient liquid water. We find that the extended exx can evaluate the EXX contribution to the stress tensor with negligible cost (< 1%) and remains highly scalable, thereby bringing us another step closer to routinely performing hybrid DFT based AIMD for large-scale condensed-phase systems across a wide range of thermodynamic conditions.