Large-Scale Electron Correlation Calculations: Rank-Reduced Full Configuration Interaction

• Published in: Journal of chemical theory and computation 2018-08, Vol.14 (8), p.4139-4150
• Main Authors: Fales, B. Scott, Seritan, Stefan, Settje, Nick F., Levine, Benjamin G., Koch, Henrik, Martínez, Todd J.
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Atomic energy levels; Configuration interaction; Determinants; Graphics processing units; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mathematical analysis; Matrix algebra; Matrix methods; Wave functions
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.8b00382

We present the rank-reduced full configuration interaction (RR-FCI) method, a variational approach for the calculation of extremely large full configuration interaction (FCI) wave functions. In this report, we show that RR-FCI can provide ground state singlet and triplet energies within kcal/mol accuracy of full CI (FCI) with computational effort scaling as the square root of the number of determinants in the CI space (compared to conventional FCI methods which scale linearly with the number of determinants). Fast graphical processing unit (GPU) accelerated projected σ = Hc matrix–vector product formation enables calculations with configuration spaces as large as 30 electrons in 30 orbitals, corresponding to an FCI calculation with over 2.4 × 1016 configurations. We apply this method in the context of complete active space configuration interaction calculations to acenes with 2–5 aromatic rings, comparing absolute energies against FCI when possible and singlet/triplet excitation energies against both density matrix renormalization group (DMRG) and experimental results. The dissociation of molecular nitrogen was also examined using both FCI and RR-FCI. In each case, we found that RR-FCI provides a low cost alternative to FCI, with particular advantages when relative energies are desired.