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Title: Making many-body interactions nearly pairwise additive: The polarized many-body expansion approach

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5125802 · OSTI ID:1604708
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
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The Many-Body Expansion (MBE) is a useful tool to simulate condensed phase chemical systems, often avoiding the steep computational cost of usual electronic structure methods. However, it often requires higher than 2-body terms to achieve quantitative accuracy. In this work, we propose the Polarized MBE (PolBE) method where each MBE energy contribution is treated as an embedding problem. In each energy term, a smaller fragment is embedded into a larger, polarized environment and only a small region is treated at the high-level of theory using embedded mean-field theory. The role of polarized environment was found to be crucial in providing quantitative accuracy at the 2-body level. PolBE accurately predicts noncovalent interaction energies for a number of systems, including CO2, water, and hydrated ion clusters, with a variety of interaction mechanisms, from weak dispersion to strong electrostatics considered in this work. We further demonstrate that the PolBE interaction energy is predominantly pairwise unlike the usual vacuum MBE that requires higher-order terms to achieve similar accuracy. We numerically show that PolBE often performs better than other widely used embedded MBE methods such as the electrostatically embedded MBE. Finally,owing to the lack of expensive diagonalization of Fock matrices and its embarrassingly parallel nature, PolBE is a promising way to access condensed phase systems with hybrid density functionals that are difficult to treat with currently available methods.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF); Multidisciplinary University Research Initiative (MURI)
Grant/Contract Number:
AC02-05CH11231; W911 NF-14-1-0359
OSTI ID:
1604708
Journal Information:
Journal of Chemical Physics, Vol. 151, Issue 19; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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