Benchmark Phaseless Auxiliary-Field Quantum Monte Carlo Method for Small Molecules
- Author(s)
- Zoran Sukurma, Martin Schlipf, Moritz Humer, Amir Taheridehkordi, Georg Kresse
- Abstract
We report a scalable Fortran implementation of the phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) and demonstrate its excellent performance and beneficial scaling with respect to system size. Furthermore, we investigate modifications of the phaseless approximation that can help to reduce the overcorrelation problems common to the ph-AFQMC. We apply the method to the 26 molecules in the HEAT set, the benzene molecule, and water clusters. We observe a mean absolute deviation of the total energy of 1.15 kcal/mol for the molecules in the HEAT set, close to chemical accuracy. For the benzene molecule, the modified algorithm despite using a single-Slater-determinant trial wavefunction yields the same accuracy as the original phaseless scheme with 400 Slater determinants. Despite these improvements, we find systematic errors for the CN, CO2, and O2 molecules that need to be addressed with more accurate trial wavefunctions. For water clusters, we find that the ph-AFQMC yields excellent binding energies that differ from CCSD(T) by typically less than 0.5 kcal/mol.
- Organisation(s)
- Computational Materials Physics
- External organisation(s)
- VASP Software GmbH
- Journal
- Journal of Chemical Theory and Computation
- Volume
- 19
- Pages
- 4921–4934
- No. of pages
- 14
- ISSN
- 1549-9618
- DOI
- https://doi.org/https://arxiv.org/abs/2303.04256v1
- Publication date
- 07-2023
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 103043 Computational physics, 103006 Chemical physics
- ASJC Scopus subject areas
- Computer Science Applications, Physical and Theoretical Chemistry
- Portal url
- https://ucris.univie.ac.at/portal/en/publications/benchmark-phaseless-auxiliaryfield-quantum-monte-carlo-method-for-small-molecules(765a9a17-e565-4789-a7ce-ff3bd8d901b3).html