Principal Domains in Local Correlation Theory

The computational efficiency of local correlation methods is strongly dependent on the size of the domain of functions used to expand local correlating orbitals such as orbital specific or pair natural orbitals. Here, we define a principal domain of order m as the subset of m one-particle functions...

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Bibliographic Details
Published inJournal of chemical theory and computation Vol. 15; no. 12; pp. 6597 - 6606
Main Author Tew, David P
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 10.12.2019
Subjects
Correlation
Domains
Greedy algorithms
Orbitals
Truncation errors
Wave functions
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Summary:The computational efficiency of local correlation methods is strongly dependent on the size of the domain of functions used to expand local correlating orbitals such as orbital specific or pair natural orbitals. Here, we define a principal domain of order m as the subset of m one-particle functions that provides the best support for a given n-electron wave function by maximizing the partial trace of the one-body reduced density matrix. Principal domains maximize the overlap between the wave function and its approximant for two-electron systems and are the domain selection equivalent of Löwdin’s natural orbitals. We present an efficient linear scaling greedy algorithm for obtaining principal domains of projected atomic orbitals and demonstrate its utility in the context of the pair natural orbital local correlation theory. We numerically determine thresholds such that the projected atomic orbital domain error is an order of magnitude smaller than the pair natural orbital truncation error.
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ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.9b00619