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Title: Correlation energy extrapolation by many-body expansion

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
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  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
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Accounting for electron correlation is required for high accuracy calculations of molecular energies. The full configuration interaction (CI) approach can fully capture the electron correlation within a given basis, but it does so at a computational expense that is impractical for all but the smallest chemical systems. In this work, a new methodology is presented to approximate configuration interaction calculations at a reduced computational expense and memory requirement, namely, the correlation energy extrapolation by many-body expansion (CEEMBE). This method combines a MBE approximation of the CI energy with an extrapolated correction obtained from CI calculations using subsets of the virtual orbitals. The extrapolation approach is inspired by, and analogous to, the method of correlation energy extrapolation by intrinsic scaling. Benchmark calculations of the new method are performed on diatomic fluorine and ozone. Finally, the method consistently achieves agreement with CI calculations to within a few mhartree and often achieves agreement to within ~1 millihartree or less, while requiring significantly less computational resources.

Research Organization:
Ames Lab., Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1347403
Report Number(s):
IS-J-9215
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 121, Issue 4; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Cited By (3)

Fantasy versus reality in fragment-based quantum chemistry journal November 2019
A review on non‐relativistic, fully numerical electronic structure calculations on atoms and diatomic molecules journal May 2019
Evaluation of full valence correlation energies and gradients journal June 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY