Speeding-up Hybrid Functional based Ab Initio Molecular Dynamics using Multiple Time-stepping and Resonance Free Thermostat

Abstract

Ab initio molecular dynamics (AIMD) based on density functional theory (DFT) has become a workhorse for studying the structure, dynamics, and reactions in condensed matter systems. Currently, AIMD simulations are primarily carried out at the level of generalized gradient approximation (GGA), which is at the 2nd rung of DFT-functionals in terms of accuracy. Hybrid DFT functionals which form the 4th rung in the accuracy ladder, are not commonly used in AIMD simulations as the computational cost involved is $100$ times or higher. To facilitate AIMD simulations with hybrid functionals, we propose here an approach that could speed up the calculations by ~30 times or more for systems with a few hundred of atoms. We demonstrate that, by achieving this significant speed up and making the compute time of hybrid functional based AIMD simulations at par with that of GGA functionals, we are able to study several complex condensed matter systems and model chemical reactions in solution with hybrid functionals that were earlier unthinkable to be performed.

arXiv comment45 pages, 9 figures, 5 tables

References in corpus (19)

• Well-Tempered Metadynamics: A Smoothly Converging and Tunable Free-Energy Method
• Localization and delocalization errors in density functional theory and implications for band-gap prediction
• The Individual and Collective Effects of Exact Exchange and Dispersion Interactions on the Ab Initio Structure of Liquid Water
• Why does hydronium diffuse faster than hydroxide in liquid water?
• Composition, structure, and stability of the rutile TiO_2(110) surface: oxygen depletion, hydroxylation, hydrogen migration and water adsorption
• Charge Localization Dynamics induced by Oxygen Vacancies on the Titania TiO${}_2$(110) Surface
• Order-N implementation of exact exchange in extended systems
• Adaptively Compressed Exchange Operator
• Local Structure Analysis in $Ab$ $Initio$ Liquid Water
• Efficient multiple time scale molecular dynamics: using colored noise thermostats to stabilize resonances
• Stochastic resonance-free multiple time-step algorithm for molecular dynamics with very large time steps
• Enabling Large-Scale Condensed-Phase Hybrid Density Functional Theory Based $Ab$ $Initio$ Molecular Dynamics I: Theory, Algorithm, and Performance
• A Systematic Study of Chloride Ion Solvation in Water using van der Waals Inclusive Hybrid Density Functional Theory
• Enhancement of DFT-calculations at Petascale: Nuclear Magnetic Resonance, Hybrid Density Functional Theory and Car-Parrinello calculations
• Hydrolysis of Cephalexin and Meropenem by New Delhi Metallo $\beta$-Lactamase: Substrate Protonation Mechanism is Drug Dependent
• Speeding-up Ab Initio Molecular Dynamics with Hybrid Functionals using Adaptively Compressed Exchange Operator based Multiple Timestepping
• Enabling Large-Scale Condensed-Phase Hybrid Density Functional Theory Based $Ab$ $Initio$ Molecular Dynamics II: Extensions to the Isobaric-Isoenthalpic and Isobaric-Isothermal Ensembles
• Faster Exact Exchange in Periodic Systems using Single-precision Arithmetic
• High-Throughput Condensed-Phase Hybrid Density Functional Theory for Large-Scale Finite-Gap Systems: The SeA Approach