Journal article
An accurate and efficient fragmentation approach via the generalized many-body expansion for density matrices
The Journal of chemical physics, Vol.159(7), 074107
08/21/2023
PMID: 37594069
Web of Science ID: WOS:001050879400004
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Abstract
With relevant chemical space growing larger and larger by the day, the ability to extend computational tractability over that larger space is of paramount importance in virtually all fields of science. The solution we aim to provide here for this issue is in the form of the generalized many-body expansion for building density matrices (GMBE-DM) based on the set-theoretical derivation with overlapping fragments, through which the energy can be obtained by a single Fock build. In combination with the purification scheme and the truncation at the one-body level, the DM-based GMBE(1)-DM-P approach shows both highly accurate absolute and relative energies for medium-to-large size water clusters with about an order of magnitude better than the corresponding energy-based GMBE(1) scheme. Simultaneously, GMBE(1)-DM-P is about an order of magnitude faster than the previously proposed MBE-DM scheme [F. Ballesteros and K. U. Lao, J. Chem. Theory Comput. 18, 179 (2022)] and is even faster than a supersystem calculation without significant parallelization to rescue the fragmentation method. For even more challenging systems including ion-water and ion-pair clusters, GMBE(1)-DM-P also performs about 3 and 30 times better than the energy-based GMBE(1) approach, respectively. In addition, this work provides the first overlapping fragmentation algorithm with a robust and effective binning scheme implemented internally in a popular quantum chemistry software package. Thus, GMBE(1)-DM-P opens a new door to accurately and efficiently describe noncovalent clusters using quantum mechanics.
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Details
- Title
- An accurate and efficient fragmentation approach via the generalized many-body expansion for density matrices
- Publication Details
- The Journal of chemical physics, Vol.159(7), 074107
- Resource Type
- Journal article
- Publisher
- AIP Publishing
- Number of pages
- 10
- Grant note
- Virginia Commonwealth University College of Humanities and SciencesDOE Office of Science User FacilityOffice of Science of the U.S. Department of Energy: BES-ERCAP0020838
This work was supported by start-up funds from the Virginia Commonwealth University College of Humanities and Sciences. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 using NERSC Award No. BES-ERCAP0020838. High Performance Computing resources provided by the High Performance Research Computing (HPRC) Core Facility at Virginia Commonwealth University (https://chipc.vcu.edu) were also used for conducting the research reported in this work.
- Identifiers
- WOS:001050879400004; 99381548017306600
- Academic Unit
- Chemistry; Hal Marcus College of Science and Engineering
- Language
- English