Frozen-Orbital and Downfolding Calculations with Auxiliary-Field Quantum Monte Carlo

Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry

doi:10.1021/ct4006486

Frozen-Orbital and Downfolding Calculations with Auxiliary-Field Quantum Monte Carlo

Journal Article · Wed Oct 23 00:00:00 EDT 2013 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/ct4006486· OSTI ID:1565149

Purwanto, Wirawan ^[1]; Zhang, Shiwei ^[1]; Krakauer, Henry ^[1]

College of William and Mary, Williamsburg, VA (United States). Dept. of Physics

We describe the implementation of the frozen-orbital and downfolding approximations in the auxiliary-field quantum Monte Carlo (AFQMC) method. These approaches can provide significant computational savings, compared to fully correlating all of the electrons. While the many-body wave function is never explicit in AFQMC, its random walkers are Slater determinants, whose orbitals may be expressed in terms of any one-particle orbital basis. It is therefore straightforward to partition the full N-particle Hilbert space into active and inactive parts to implement the frozen-orbital method. In the frozen-core approximation, for example, the core electrons can be eliminated in the correlated part of the calculations, greatly increasing the computational efficiency, especially for heavy atoms. Scalar relativistic effects are easily included using the Douglas–Kroll–Hess theory. Using this method, we obtain a way to effectively eliminate the error due to single-projector, norm-conserving pseudopotentials in AFQMC. We also illustrate a generalization of the frozen-orbital approach that downfolds high-energy basis states to a physically relevant low-energy sector, which allows a systematic approach to produce realistic model Hamiltonians to further increase efficiency for extended systems.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1565149

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 11 Vol. 9; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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