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The complete active space self-consistent field (CASSCF) method is the principal approach employed for studying strongly correlated systems. However, exact CASSCF can only be performed on small active spaces of ~20 electrons in ~20 orbitals…

Computational Physics · Physics 2021-12-22 Daniel S. Levine , Diptarka Hait , Norm M. Tubman , Susi Lehtola , K. Birgitta Whaley , Martin Head-Gordon

The efficiency of the recently proposed iCIPT2 [iterative configuration interaction (iCI) with selection and second-order perturbation theory (PT2); J. Chem. Theory Comput. 16, 2296 (2020)] for strongly correlated electrons is further…

Chemical Physics · Physics 2020-11-19 Ning Zhang , Wenjian Liu , Mark R. Hoffmann

Analytic energy gradients are presented for a variational two-electron reduced-density-matrix-driven complete active space self-consistent field (v2RDM-CASSCF) procedure that employs the density-fitting (DF) approximation to the…

Chemical Physics · Physics 2018-11-29 J. Wayne Mullinax , Evgeny Epifanovsky , Gergely Gidofalvi , A. Eugene DePrince

Even when starting with a very poor initial guess, the iterative configuration interaction (iCI) approach can converge from above to full CI very quickly by constructing and diagonalizing a small Hamiltonian matrix at each…

Chemical Physics · Physics 2020-01-07 Ning Zhang , Wenjian Liu , Mark R. Hoffmann

Traditional multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) methods are based on a single orthonormal orbital basis (OB). For atoms with complicated shell structures, a large OB is needed to saturate all the…

Atomic Physics · Physics 2015-06-12 S. Verdebout , P. Rynkun , P. Jönsson , G. Gaigalas , C. Froese Fischer , M. Godefroid

Recently, a new distributed implementation of the full configuration interaction (FCI) method has been reported [Gao et al. J. Chem Theory Comput. 2024, 20, 1185]. Thanks to a hybrid parallelization scheme, the authors were able to compute…

Recent advances in selected CI, including the adaptive sampling configuration interaction (ASCI) algorithm and its heat bath extension, have made the ASCI approach competitive with the most accurate techniques available, and hence an…

We study several approaches to orbital optimization in selected configuration interaction plus perturbation theory (SCI+PT) methods, and test them on the ground and excited states of three molecules using the semistochastic heatbath…

Chemical Physics · Physics 2021-07-14 Yuan Yao , C. J. Umrigar

Quantum-selected configuration interaction (QSCI) is a novel quantum-classical hybrid algorithm for quantum chemistry calculations. This method identifies electron configurations having large weights for the target state using quantum…

Chemical Physics · Physics 2025-03-31 Soichi Shirai , Shih-Yen Tseng , Hokuto Iwakiri , Takahiro Horiba , Hirotoshi Hirai , Sho Koh

We consider gradient descent and quasi-Newton algorithms to optimize the full configuration interaction (FCI) ground state wavefunction starting from an arbitrary reference state $|0 \rangle$. We show that the energies obtained along the…

Chemical Physics · Physics 2021-02-03 Carlos A. Jiménez-Hoyos

Selected configuration interaction (SCI) methods, when complemented with a second-order perturbative correction, provide near full configuration interaction (FCI) quality energies with only a small fraction of the Slater determinants of the…

Selected configuration interaction (sCI) methods including second-order perturbative corrections provide near full CI (FCI) quality energies with only a small fraction of the determinants of the FCI space. Here, we introduce both a…

Chemical Physics · Physics 2018-08-09 Yann Garniron , Anthony Scemama , Emmanuel Giner , Michel Caffarel , Pierre-François Loos

We introduce a new augmented adaptation of the recently developed full coupled-cluster reduction (FCCR) with a second-order perturbative correction, abbreviated as FCCR(2). FCCR is a selected coupled-cluster expansion aimed at optimally…

Chemical Physics · Physics 2020-11-06 Enhua Xu , Motoyuki Uejima , Seiichiro L. Ten-no

The interplay between advances in stochastic and deterministic algorithms has recently led to development of interesting new selected configuration interaction (SCI) methods for solving the many body Schr\"{o}dinger equation. The…

Strongly Correlated Electrons · Physics 2018-08-08 Norm M. Tubman , Daniel S. Levine , Diptarka Hait , Martin Head-Gordon , K. Birgitta Whaley

In this paper, we study the nuclear gradients of heat bath configuration interaction self-consistent field (HCISCF) wave functions and use them to optimize molecular geometries for various molecules. We show that the HCISCF nuclear…

Chemical Physics · Physics 2022-09-14 James E. T. Smith , Joonho Lee , Sandeep Sharma

We introduce the pCI software package for high-precision atomic structure calculations. The standard method of calculation is based on the configuration interaction (CI) method to describe valence correlations, but can be extended to attain…

In this work, we develop a new orbital optimization approach, perturbative Super-CI (Super-CIPT), for the two-component complete active space self-consistent field (2C-CASSCF) method. By variationally optimizing spinor orbitals and…

Chemical Physics · Physics 2026-03-04 Yang Guo , Achintya Kumar Dutta

We present a new high-performance configuration interaction code optimally designed for the calculation of the lowest energy eigenstates of a few electrons in semiconductor quantum dots (also called artificial atoms) in the strong…

Strongly Correlated Electrons · Physics 2007-05-23 Massimo Rontani , Carlo Cavazzoni , Devis Bellucci , Guido Goldoni

Based on self-consistent field (SCF) atomic mean-field (amf) quantities, we present two simple, yet computationally efficient and numerically accurate matrix-algebraic approaches to correct both scalar-relativistic \textit{and} spin-orbit…

Chemical Physics · Physics 2023-02-03 Stefan Knecht , Michal Repisky , Hans Jørgen Aagaard Jensen , Trond Saue

A model subspace configuration interaction method is developed to obtain chemically accurate electron correlations by diagonalising a very compact effective Hamiltonian of realistic molecule. The construction of the effective Hamiltonian is…

Chemical Physics · Physics 2022-10-18 Jiasheng Li , Jun Yang
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