Analytic Gradients for Restricted Active Space Second-order Perturbation Theory (RASPT2)

Nishimoto, Yoshio

doi:10.26434/chemrxiv.14197457

Cited by 1 publication

(1 citation statement)

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“…36 Implementations for nuclear gradients and non-adiabatic coupling vectors at the CASSCF and CASPT2 level of theory have been presented by various groups. [37][38][39][40][41] Carter et al have used the procedure in linear-scaling and localized multi-reference configuration interaction (MRCI) theory, 42,43 while Lehtola et al have used it for studies on the Perdew-Zunger self-interaction correction 44,45 and the perfect pairing hierarchy, 46 which is a family of truncated coupled-cluster (CC) methods. Other types of CC theories have seen use of Cholesky decomposed ERIs by a large number of groups.…”

Section: Literature Reviewmentioning

confidence: 99%

The versatility of Cholesky decomposition in electronic structure theory

Pedersen

Lehtola

Galván

et al. 2023

Preprint

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The resolution-of-the-identity (RI) or density fitting (DF) approximation for the electron repulsion integrals (ERIs) has become a standard component of accelerated and reduced-scaling implementations of first-principles Gaussian- type orbital electronic-structure methods. The Cholesky decomposition (CD) of the ERIs has also become increasingly deployed across quantum chemistry packages in the last decade, even though its early applications were mostly limited to high-accuracy methods such as coupled-cluster theory and multi-configurational approaches. Starting with a summary of the basic theory underpinning both the CD and RI/DF approximations, thus underlining the extremely close relation of the CD and RI/DF techniques, we provide a brief and largely chronological review of the evolution of the CD approach from its birth in 1977 to its current state. In addition to being a purely numerical procedure for handling ERIs, thus providing robust and computationally efficient approximations to the exact ERIs that have been found increasingly useful on modern computer platforms, CD also offers highly accurate approaches for generating auxiliary basis sets for the RI/DF approximation on the fly, as the two approaches have a deep mathematical connection. In this review, we aim to provide a concise reference of the main techniques employed in various CD approaches in electronic structure theory, to exemplify the connection between the CD and RI/DF approaches, and to clarify the state of the art to guide new implementations of CD approaches across electronic structure programs.

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