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Hylleraas-Configuration Interaction (Hy-CI) calculations on the ground $1^1$S state of helium atom are presented using s-, p-, d-, and f-Slater orbitals of both real and complex form. Techniques of construction of adapted configurations,…

Atomic Physics · Physics 2016-01-29 Maria Belen Ruiz

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

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

In this work, we investigate the possibility of improving multireference-driven coupled cluster (CC) approaches with an algorithm that iteratively combines complete active space (CAS) calculations with tailored CC and externally corrected…

Chemical Physics · Physics 2025-03-06 Robin Feldmann , Max Mörchen , Jakub Lang , Michał Lesiuk , Markus Reiher

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…

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

We present a new second order complete active space self-consistent field implementation to converge wavefunctions for both large active spaces and large atomic orbital (AO) bases. Our algorithm decouples the active space wavefunction…

Chemical Physics · Physics 2017-08-23 Qiming Sun , Jun Yang , Garnet Kin-Lic Chan

We present an efficient orbital optimization procedure that combines the highly GPU accelerated, spin-adapted density matrix renormalization group (DMRG) method with the complete active space self-consistent field (CAS-SCF) approach for…

In this work we demonstrate how to compute the one- and two-body reduced density matrices within the spin-adapted full configuration interaction quantum Monte Carlo (FCIQMC) method, which is based on the graphical unitary group approach…

Chemical Physics · Physics 2021-09-27 Werner Dobrautz , Oskar Weser , Nikolay Bogdanov , Ali Alavi , Giovanni Li Manni

By combining Hartree-Fock with a neural-network-supported quantum-cluster solver proposed recently in the context of solid-state lattice models, we formulate a scheme for selective neural-network configuration interaction (NNCI)…

Accurately describing strongly correlated systems with affordable quantum resources remains a central challenge for quantum chemistry applications on near and intermediate-term quantum computers. The localized active space self-consistent…

Accurate computation of non-covalent, intermolecular interaction energies is important to understand various chemical phenomena, and quantum computers are anticipated to accelerate it. Although the state-of-the-art quantum computers are…

Quantum Physics · Physics 2025-12-29 Yuhei Tachi , Akihiko Arakawa , Taisei Osawa , Masayoshi Terabe , Kenji Sugisaki

We propose a novel partitioning of the Hilbert space, hierarchy configuration interaction (hCI), where the excitation degree (with respect to a given reference determinant) and the seniority number (i.e., the number of unpaired electrons)…

Chemical Physics · Physics 2022-05-12 Fábris Kossoski , Yann Damour , Pierre-François Loos

Iron-sulfur clusters comprise an important functional motif of the catalytic centers of biological systems, capable of enabling important chemical transformations at ambient conditions. This remarkable capability derives from a notoriously…

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

In the present letter, it is demonstrated how full configuration interaction (FCI) results in extended basis sets may be obtained to within sub-kJ/mol accuracy by decomposing the energy in terms of many-body expansions in the virtual…

Chemical Physics · Physics 2017-09-15 Janus J. Eriksen , Filippo Lipparini , Jürgen Gauss

We identify the dominant computational cost within the recently introduced stochastic and internally contracted FCIQMC-NEVPT2 method for large active space sizes. This arises from the contribution to the four-body intermediates arising from…

Chemical Physics · Physics 2020-10-05 James J. Halson , Robert J. Anderson , George H. Booth

We introduce vibrational heat-bath configuration interaction (VHCI) as an accurate and efficient method for calculating vibrational eigenstates of anharmonic systems. Inspired by its origin in electronic structure theory, VHCI is a selected…

Chemical Physics · Physics 2021-03-17 Jonathan H. Fetherolf , Timothy C. Berkelbach

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 present the time-dependent complete-active-space self-consistent-field (TD-CASSCF) method to simulate multielectron dynamics in ultrafast intense laser fields from the first principles. While based on multiconfiguration expansion, it…

Atomic Physics · Physics 2018-04-24 Takeshi Sato , Yuki Orimo , Takuma Teramura , Oyunbileg Tugs , Kenichi L. Ishikawa