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Title: Communication: Improved pair approximations in local coupled-cluster methods

In local coupled cluster treatments the electron pairs can be classified according to the magnitude of their energy contributions or distances into strong, close, weak, and distant pairs. Different approximations are introduced for the latter three classes. In this communication, an improved simplified treatment of close and weak pairs is proposed, which is based on long-range cancellations of individually slowly decaying contributions in the amplitude equations. Benchmark calculations for correlation, reaction, and activation energies demonstrate that these approximations work extremely well, while pair approximations based on local second-order Møller-Plesset theory can lead to errors that are 1-2 orders of magnitude larger.
Authors:
;  [1] ;  [2]
  1. Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany)
  2. Institute for Physical and Theoretical Chemistry, Universität Regensburg, Universitätsstrasse 31, D-93040 Regensburg (Germany)
Publication Date:
OSTI Identifier:
22415548
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 12; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ACTIVATION ENERGY; AMPLITUDES; APPROXIMATIONS; BENCHMARKS; CANCELLATION; CORRELATIONS; ELECTRON PAIRS; EQUATIONS