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Author Manzer, Samuel ♦ Horn, Paul R. ♦ Mardirossian, Narbe ♦ Head-Gordon, Martin
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ MATHEMATICAL METHODS AND COMPUTING ♦ ACCURACY ♦ ALGORITHMS ♦ DENSITY FUNCTIONAL METHOD ♦ EFFICIENCY ♦ EVALUATION ♦ GRAPHENE ♦ HYDROGEN ♦ MOLECULAR ORBITAL METHOD
Abstract Construction of the exact exchange matrix, K, is typically the rate-determining step in hybrid density functional theory, and therefore, new approaches with increased efficiency are highly desirable. We present a framework with potential for greatly improved efficiency by computing a compressed exchange matrix that yields the exact exchange energy, gradient, and direct inversion of the iterative subspace (DIIS) error vector. The compressed exchange matrix is constructed with one index in the compact molecular orbital basis and the other index in the full atomic orbital basis. To illustrate the advantages, we present a practical algorithm that uses this framework in conjunction with the resolution of the identity (RI) approximation. We demonstrate that convergence using this method, referred to hereafter as occupied orbital RI-K (occ-RI-K), in combination with the DIIS algorithm is well-behaved, that the accuracy of computed energetics is excellent (identical to conventional RI-K), and that significant speedups can be obtained over existing integral-direct and RI-K methods. For a 4400 basis function C{sub 68}H{sub 22} hydrogen-terminated graphene fragment, our algorithm yields a 14 × speedup over the conventional algorithm and a speedup of 3.3 × over RI-K.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2015-07-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 143
Issue Number 2


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