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Title: The Jastrow antisymmetric geminal power in Hilbert space: Theory, benchmarking, and application to a novel transition state

The Jastrow-modified antisymmetric geminal power (JAGP) ansatz in Hilbert space successfully overcomes two key failings of other pairing theories, namely, a lack of inter-pair correlations and a lack of multiple resonance structures, while maintaining a polynomially scaling cost, variational energies, and size consistency. Here, we present efficient quantum Monte Carlo algorithms that evaluate and optimize the JAGP energy for a cost that scales as the fifth power of the system size. We demonstrate the JAGP’s ability to describe both static and dynamic correlation by applying it to bond stretching in H{sub 2}O, C{sub 2}, and N{sub 2} as well as to a novel, multi-reference transition state of ethene. JAGP’s accuracy in these systems outperforms even the most sophisticated single-reference methods and approaches that of exponentially scaling active space methods.
Authors:
 [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22251413
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 19; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; ALGORITHMS; ETHYLENE; HILBERT SPACE; MONTE CARLO METHOD; POLYNOMIALS