Toward Large-Scale AFQMC Calculations: Large Time Step Auxiliary-Field Quantum Monte Carlo

Author(s)
Zoran Sukurma, Martin Schlipf, Moritz Humer, Amir Taheridehkordi, Georg Kresse
Abstract

We report modifications of the ph-AFQMC algorithm that allow the use of large time steps and reliable time step extrapolation. Our modified algorithm eliminates size-consistency errors present in the standard algorithm when large time steps are employed. We investigate various methods to approximate the exponential of the one-body operator within the AFQMC framework, distinctly demonstrating the superiority of Krylov methods over the conventional Taylor expansion. We assess various propagators within AFQMC and demonstrate that the Split-2 propagator is the optimal method, exhibiting the smallest time-step errors. For the HEAT set molecules, the time-step extrapolated energies deviate on average by only 0.19 kcal/mol from the accurate small time-step energies. For small water clusters, we obtain accurate complete basis-set binding energies using time-step extrapolation with a mean absolute error of 0.07 kcal/mol compared to CCSD(T). Using large time-step ph-AFQMC for the N2 dimer, we show that accurate bond lengths can be obtained while reducing CPU time by an order of magnitude.

Organisation(s)
Computational Materials Physics
External organisation(s)
VASP Software GmbH
Journal
Journal of Chemical Theory and Computation
Volume
20
Pages
4205–4217
No. of pages
13
ISSN
1549-9618
DOI
https://doi.org/10.48550/arXiv.2403.02542
Publication date
05-2024
Peer reviewed
Yes
Austrian Fields of Science 2012
103006 Chemical physics, 103043 Computational physics
ASJC Scopus subject areas
Computer Science Applications, Physical and Theoretical Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/4225e3dd-2b3b-4b5c-bd05-8b51d424d3e8