A black-box, general purpose quadratic self-consistent field code with and without Cholesky decomposition of the two-electron integrals

Nottoli, Tommaso; Gauß, Jürgen; Lipparini, Filippo

doi:10.1080/00268976.2021.1974590

Cited by 16 publications

(16 citation statements)

References 54 publications

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“…The same code was used for the CCSD(T)(a)* and single-point UCCSD(T) calculations with the triple-ζ basis set. In cfour , we relied on the QC-SCF algorithm with the correct occupation number set, and a SCF convergence threshold of 10 –9 or 10 –10 au. All CIS(D), ADC(2), and CC2 calculations have been performed with turbomole , using the aug -cc-pVTZ basis set and applying the RI approach with the corresponding auxiliary basis.…”

Section: Computational Detailsmentioning

confidence: 99%

Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet Gap

Loos,

Lipparini,

Jacquemin

2023

J. Phys. Chem. Lett.

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Section: Computational Detailsmentioning

confidence: 99%

Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet Gap

Loos,

Lipparini,

Jacquemin

2023

J. Phys. Chem. Lett.

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“…In parallel with this work, Lew- The CD procedure is now starting to be incorporated to its full extent in various program packages beyond OpenMolcas 50 and e T . 34 Nottoli et al, 51 for example, have recently reported two implementations in the CFOUR software package 52 using CD ERIs. First for a quadratically convergent SCF (QCSCF) implementation, 51 and secondly for a second-order multi-configuration SCF (MCSCF) implementation.…”

Section: Eris and Related Tensorsmentioning

confidence: 99%

“…34 Nottoli et al, 51 for example, have recently reported two implementations in the CFOUR software package 52 using CD ERIs. First for a quadratically convergent SCF (QCSCF) implementation, 51 and secondly for a second-order multi-configuration SCF (MCSCF) implementation. 53 For the latter implementation, they report a significant reduction in the computational cost, reduced memory requirements, and an improved parallel performance.…”

Section: Eris and Related Tensorsmentioning

confidence: 99%

The versatility of Cholesky decomposition of electron repulsion integrals

Pedersen

Galván

Lindh

2023

Preprint

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Over the past three decades, the resolution-of-the-identity (RI) approximation of electron repulsion integrals (ERIs) over Gaussian-type orbitals has become a stan- dard component of accelerated and reduced-scaling implementations of first-principles electronic-structure methods. For the first two decades, the closely related approach based on Cholesky decomposition (CD) of the ERIs lived a more secluded life, fo- cusing mainly on high-accuracy methods such as coupled-cluster theory and multi- configurational approaches. In the past decade, however, the CD technique has been increasingly deployed across quantum chemistry as a numerically robust, computation- ally efficient, and highly accurate approach to on-the-fly generation of auxiliary basis sets for the RI approximation. Starting with a summary of the basic theory underpin- ning both the CD and RI approximations, we provide a brief and largely chronological review of the evolution of the CD approach from its birth in 1977 as a purely numerical procedure for handling ERIs to its current state as the perhaps most powerful on-the-fly generator of auxiliary basis sets.

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“…The electronic energy E 0 , and its first (gradient g) and second derivatives (Hessian H) with respect to all variations x in the wave function parameters must then be computed. In the TRAH algorithm, 22,25,26 the update of the current parameters is obtained by searching for the lowest eigenvalue and its corresponding eigenvector of the scaled augmented Hessian (AH) matrix…”

Section: B Trah Optimization Of Casscf Wave Functionsmentioning

confidence: 99%

A trust-region augmented Hessian implementation for state-specific and state-averaged CASSCF wave functions

Helmich-Paris

2022

Preprint

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In this work, we present a one-step second-order converger for state-specific (SS) and state-averaged (SA) complete active space self-consistent field (CASSCF) wave functions. Robust convergence is achieved through step restrictions using a trust-region augmented Hessian (TRAH) algorithm. To avoid numerical instabilities, an exponential parametrization of variational configuration parameters is employed, which works with a nonredundant orthogonal complement basis. This is a common approach for SS-CASSCF and is extended to SA-CASSCF wave functions, in this work. Our implementation is integral direct and based on intermediates that are formulated either in the sparse atomic-orbital or small active molecular-orbital basis. Thus, it benefits from a combination with efficient integral decomposition techniques, such as the resolution-of-the-identity or the chain-of-spheres for exchange approximations. This facilitates calculations on large molecules such as a Ni(II) complex with 231 atoms and 5154 basis functions. The runtime performance of TRAH-CASSCF is competitive with other state-of-the-art implementations of approximate and full second-order algorithms.In comparison with a sophisticated first-order converger, TRAH-CASSCF calculations usually take more iterations to reach convergence and, thus, have longer runtimes. However, TRAH-CASSCF calculations still converge reliably to a true minimum even if the first-order algorithm fails.

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A black-box, general purpose quadratic self-consistent field code with and without Cholesky decomposition of the two-electron integrals

Cited by 16 publications

References 54 publications

Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet Gap

Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet Gap

The versatility of Cholesky decomposition of electron repulsion integrals

A trust-region augmented Hessian implementation for state-specific and state-averaged CASSCF wave functions

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