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Asymmetric Density Fitting with Modified Cholesky Decomposition Applied to Second-Order Electron Propagator

2020; American Chemical Society; Volume: 16; Issue: 3 Linguagem: Inglês

10.1021/acs.jctc.9b01215

1549-9626

Juan Felipe Huan Lew-Yee, Roberto Flores‐Moreno, José Luis Morales, Jorge M. del Campo,

Photochemistry and Electron Transfer Studies

Computation of molecular orbital electron repulsion integrals (MO-ERIs) as a transformation from atomic orbital ERIs (AO-ERIs) is the bottleneck of second-order electron propagator calculations when a single orbital is studied. In this contribution, asymmetric density fitting is combined with modified Cholesky decomposition to generate efficiently the required MO-ERIs. The key point of the presented algorithms is to keep track of integrals through partial contractions performed on three-center AO-ERIs; these contractions are stored in RAM instead of the AO-ERIs. Two implementations are provided, an in-core, which reduces the arithmetic and memory scaling factors as compared to the four-center AO-ERIs contraction method, and a semidirect, which overcomes memory limitations by evaluating antisymmetrized MO-ERIs in batches. On the numerical side, the proposed approach is fast and stable. The bad effects due to ill conditioning, namely, several negative and close to zero eigenvalues due to machine round off errors of the matrix associated with the density fitting process, are effectively controlled by means of a modified Cholesky factorization that avoids the matrix inversion needed to perform the asymmetrical density fitting implementation. The numerical experience presented shows that the in-core implementation is highly competitive to perform calculations on medium and large basis sets, while the semidirect implementation has small variations in time by changes in the available memory. The general applicability is illustrated on a set of selected relatively large-size molecules.