Local Embedding and Effective Downfolding in the Auxiliary-Field Quantum Monte Carlo Method

Eskridge, Brandon; Krakauer, Henry; Zhang, Shiwei

doi:10.1021/acs.jctc.8b01244

Local Embedding and Effective Downfolding in the Auxiliary-Field Quantum Monte Carlo Method

Journal Article · Tue Jun 25 00:00:00 EDT 2019 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.8b01244· OSTI ID:1544771

^[1]; Krakauer, Henry ^[2]; Zhang, Shiwei ^[3]

College of William and Mary, Williamsburg, VA (United States); College of William & Mary
College of William and Mary, Williamsburg, VA (United States)
College of William and Mary, Williamsburg, VA (United States); The Flatiron Institute, New York, NY (United States)

A local embedding and effective downfolding scheme has been developed and implemented in the auxiliary-field quantum Monte Carlo (AFQMC) method. A local cluster in which electrons are fully correlated is defined, and the frozen orbital method is used on the remainder of the system to construct an effective Hamiltonian, which operates within the local cluster. Local embedding, which involves only the occupied sector, has previously been employed in the context of Co/graphene. Here, the methodology is extended in order to allow for effective downfolding of the virtual sector, thus allowing for significant reduction in the computational effort required for AFQMC calculations. The system size, which can be feasibly treated with AFQMC, is therefore greatly extended as only a single local cluster is explicitly correlated at the AFQMC level of theory. The approximation is controlled by the separate choice of the spatial size of the active occupied region (Ro) and of the active virtual region (Rv). In conclusion, the systematic dependence of the AFQMC energy on Ro and Rv is investigated, and it is found that relative AFQMC energies of physical and chemical interest converge rapidly to the full AFQMC treatment (i.e., using no embedding or downfolding).

View Accepted Manuscript (DOE)

Research Organization:: College of William and Mary, Williamsburg, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0001303

OSTI ID:: 1544771

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 7 Vol. 15; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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