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Projector-Based Quantum Embedding for Molecular Systems: An Investigation of Three Partitioning Approaches

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3]
  1. Ames Lab., Ames, IA (United States)
  2. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate
+ Show Author Affiliations
Projector-based embedding is a relatively recent addition to the collection of methods that seek to utilize chemical locality to provide improved computational efficiency. This work considers the interactions between the different proposed procedures for this method and their effects on the accuracy of the results. The interplay between the embedded background, projector type, partitioning scheme, and level of atomic orbital (AO) truncation are investigated on a selection of reactions from the literature. The Huzinaga projection approach proves to be more reliable than the level-shift projection when paired with other procedural options. Active subsystem partitioning from the subsystem projected AO decomposition (SPADE) procedure proves slightly better than the combination of Pipek-Mezey localization and Mulliken population screening (PMM). Along with these two options, a new partitioning criteria is proposed based on subsystem von Neumann entropy and the related subsystem orbital occupancy. This new method overlaps with the previous PMM method, but the screening process is computationally simpler. Finally, AO truncation proves to be a robust option for the tested systems when paired with the Huzinaga projection, with satisfactory results being acquired at even the most severe truncation level.
Research Organization:
Ames Laboratory (AMES), Ames, IA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
Exascale Computing Project; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-07CH11358; AC05-76RL01830
OSTI ID:
1810409
Alternate ID(s):
OSTI ID: 1817631
Report Number(s):
IS-J--10,561; PNNL-SA-161824
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 29 Vol. 125; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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