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Title: Implementation of analytic gradients for CCSD and EOM-CCSD using Cholesky decomposition of the electron-repulsion integrals and their derivatives: Theory and benchmarks

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5100022 · OSTI ID:1613023
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Q-Chem, Inc., Pleasanton, CA (United States); Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry; DOE/OSTI
  2. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
  3. Johannes Gutenberg Univ., Mainz (Germany)
  4. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry; Johannes Gutenberg Univ., Mainz (Germany)
+ Show Author Affiliations

We present a general formulation of analytic nuclear gradients for the coupled-cluster with single and double substitution (CCSD) and equation-of-motion (EOM) CCSD energies computed using Cholesky decomposition (CD) representations of the electron repulsion integrals. By rewriting the correlated energy and response equations such that the storage of the largest four-index intermediates is eliminated, CD leads to a significant reduction in disk storage requirements, reduced I/O penalties, and an improved parallel performance. CD thus extends the scope of the systems that can be treated by (EOM-)CCSD methods, although analytic gradients in the framework of CD are needed to extend the applicability of (EOM-)CCSD methods in the context of geometry optimizations. This paper presents a formulation of analytic (EOM-)CCSD gradient within the CD framework and reports on the salient details of the corresponding implementation. The accuracy and the capabilities of analytic CD-based (EOM-)CCSD gradients are illustrated by benchmark calculations and several illustrative examples.

Research Organization:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0018910
OSTI ID:
1613023
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 151; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

On the accurate reproduction of strongly repulsive interatomic potentials text January 2019
NWChem: Past, Present, and Future text January 2020
Extension of frozen natural orbital approximation to open-shell references: Theory, implementation, and application to single-molecule magnets journal January 2020
Accurate reproduction of strongly repulsive interatomic potentials journal March 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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