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The correction of the self-interaction error (SIE) that is inherent to all standard density functional theory (DFT) calculations is an object of increasing interest. In this article we apply the very recently developed Fermi-orbital based…

Computational Physics · Physics 2016-01-20 Torsten Hahn , Simon Liebing , Jens Kortus , Mark R. Pederson

We present a novel theoretical scheme for orbital relaxation in configuration interaction singles (CIS) based on a perturbative treatment of its electronic Hessian, whose analytical derivation is also established in this work. The proposed…

Chemical Physics · Physics 2026-03-06 Takashi Tsuchimochi

We compute highly accurate first principle based \textit{ab initio} adiabatic potential energy surfaces (PESs) using State-Averaged Multi-Configurational Self-Consistent Field (SA-MCSCF) followed by internally contracted Multi-Reference…

Chemical Physics · Physics 2026-03-10 Avik Guchait , Gourhari Jana , Satyam Ravi , Koushik Naskar , Satrajit Adhikari

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

The description of electronic exchange--correlation effects is of paramount importance for many applications in physics, chemistry, and beyond. In a recent Letter, Dornheim \textit{et al.} [\textit{Phys. Rev. Lett.}~\textbf{125}, 235001…

Plasma Physics · Physics 2021-04-07 Tobias Dornheim , Zhandos A. Moldabekov , Panagiotis Tolias

The semistochastic heat-bath configuration interaction (SHCI) method is a selected configuration interaction plus perturbation theory method that has provided near-full configuration interaction (FCI) levels of accuracy for many systems…

Chemical Physics · Physics 2021-11-30 Yuan Yao , Emmanuel Giner , Tyler A. Anderson , Julien Toulouse , C. J. Umrigar

We derive analytical nuclear gradients for state-averaged orbital-optimized configuration interaction singles (SACIS) and its spin-projected extension (SAECIS), enabling efficient geometry optimization and minimum-energy conical…

Chemical Physics · Physics 2026-04-15 Takashi Tsuchimochi

An active space variational calculation of the 2-electron reduced density matrix (2-RDM) is derived and implemented where the active orbitals are correlated within the pair approximation. The pair approximation considers only doubly…

Chemical Physics · Physics 2020-10-13 Kade Head-Marsden , David A. Mazziotti

We investigate configuration-interaction (CI) calculations on a basis of molecular orbitals generated by preliminary density-functional theory (DFT) calculations. We use this CI/DFT framework to improve the modeling of core-excited states…

Chemical Physics · Physics 2025-09-11 Giorgio Visentin , Francois Mauger

The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density…

Mesoscale and Nanoscale Physics · Physics 2017-03-07 Zhenfei Liu , David A. Egger , Sivan Refaely-Abramson , Leeor Kronik , Jeffrey B. Neaton

The recent development of the density matrix renormalization group (DMRG) method in multireference quantum chemistry makes it practical to evaluate static correlation in a large active space, while dynamic correlation provides a critical…

Strongly Correlated Electrons · Physics 2020-08-20 Zhen Luo , Yingjin Ma , Xicun Wang , Haibo Ma

We present a study of fixed and partial-node approximations in Slater determinant basis sets, using full configuration interaction quantum Monte Carlo (FCIQMC) to perform sampling. Walker annihilation in the FCIQMC method allows…

Chemical Physics · Physics 2021-09-27 Nick S. Blunt

In this contribution, we present the implementation of a second-order CASSCF algorithm in conjunction with the Cholesky decomposition of the two-electron repulsion integrals. The algorithm, called Norm-Extended Optimization, guarantees…

Chemical Physics · Physics 2021-04-09 Tommaso Nottoli , Jürgen Gauss , Filippo Lipparini

Semilocal density-functional approximations (DFAs), including the state-of-the-art SCAN functional, are plagued by the self-interaction error (SIE). While this error is explicitly defined only for one-electron systems, it has inspired the…

Materials Science · Physics 2024-01-23 Sheng Bi , Christian Carbogno , Igor Ying Zhang , Matthias Scheffler

We propose a size-consistent generalization of the recently developed spin-extended configuration interaction with singles and doubles (ECISD), where a CI wave function is explicitly spin-projected. The size-consistent effect is effectively…

Chemical Physics · Physics 2017-01-25 Takashi Tsuchimochi , Seiichiro Ten-no

We present a wide-reaching revamp of the generalized many-body expanded full configuration interaction (MBE-FCI) method. First, we outline how to automatize the selection of reference active spaces whereby the inherent bias introduced…

Chemical Physics · Physics 2024-06-18 Jonas Greiner , Jürgen Gauss , Janus J. Eriksen

We present an \emph{Effective Static Approximation} (ESA) to the local field correction (LFC) of the electron gas that enables highly accurate calculations of electronic properties like the dynamic structure factor $S(q,\omega)$, the static…

The convergence property of a stochastic algorithm for the self-consistent field (SCF) calculations of electron structures is studied. The algorithm is formulated by rewriting the electron charges as a trace/diagonal of a matrix function,…

Numerical Analysis · Mathematics 2023-04-20 Taehee Ko , Xiantao Li

Three fully variational formulations of the complete-active space coupled-cluster (CASCC) method are derived. The formulations include the ability to approximate the model vectors by smooth manifolds, thereby opening up the possibility for…

Chemical Physics · Physics 2023-07-12 Simen Kvaal

In the past decade, natural orbital functional (NOF) approximations have emerged as prominent tools for characterizing electron correlation. Despite their effectiveness, these approaches, which rely on natural orbitals and their associated…

Chemical Physics · Physics 2024-04-19 Ion Mitxelena , Mario Piris
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