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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

State-specific complete active space self-consistent field (SS-CASSCF) theory has emerged as a promising route to accurately predict electronically excited energy surfaces away from molecular equilibria. However, its accuracy and…

Chemical Physics · Physics 2024-02-21 Sandra Saade , Hugh G. A. Burton

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

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…

Unitary Coupled Cluster (UCC) theory is a promising variational method for electronic structure calculations, especially for strongly correlated systems and quantum computers. However, its practical application is limited by the steep…

Chemical Physics · Physics 2026-02-05 Prateek Vaish , Brenda Rubenstein

The recently developed localized orbital scaling correction (LOSC) method shows the ability to systematically and size-consistently reduce the delocalization error existing in conventional density functional approximations (DFAs). Applying…

Chemical Physics · Physics 2020-10-19 Yuncai Mei , Zehua Chen , Weitao Yang

Modeling chemical reactions with quantum chemical methods is challenging when the electronic structure varies significantly throughout the reaction, as well as when electronic excited states are involved. Multireference methods such as…

The approximate atomic self-interaction corrections (ASIC) method to density functional theory is put to the test by calculating the exchange interaction for a number of prototypical materials, critical to local exchange and correlation…

Materials Science · Physics 2009-11-13 A. Akande , S. Sanvito

Strong correlation can be essentially captured with multireference wavefunction methods such as complete active space self-consistent field (CASSCF) or density matrix renormalization group (DMRG). Still, an accurate description of the…

Strongly Correlated Electrons · Physics 2022-04-06 Daria Drwal , Pavel Beran , Michał Hapka , Marcin Modrzejewski , Adam Sokół , Libor Veis , Katarzyna Pernal

Methods for correcting residual energy errors of configuration interaction (CI) calculations of molecules and other electronic systems are discussed based on the assumption that the energy defect can be mapped onto atomic regions. The…

Chemical Physics · Physics 2022-10-05 Jerry L. Whitten

The quantum-selected configuration interaction (QSCI) method is a promising approach for large-scale quantum chemical calculations on currently available quantum hardware. However, its naive implementation lacks size consistency, which is…

Quantum Physics · Physics 2026-01-06 Kenji Sugisaki

We present a modification of the $\Delta$SCF method of calculating energies of excited states, in order to make it applicable to resonance calculations of molecules adsorbed on metal surfaces, where the molecular orbitals are highly…

Materials Science · Physics 2009-03-06 Jeppe Gavnholt , Thomas Olsen , Mads Engelund , Jakob Schiøtz

In a recent paper, we proposed the adaptive shift method for correcting the undersampling bias of the initiator-FCIQMC. The method allows faster convergence with the number of walkers to the FCI limit than the normal initiator method,…

Computational Physics · Physics 2021-02-03 Khaldoon Ghanem , Kai Guther , Ali Alavi

We propose an efficient algorithm for the recently published electron/hole-transfer Dynamical-weighted State-averaged Constrained CASSCF (eDSC/hDSC) method studying charge transfer states and D$_1$-D$_0$ crossings for systems with odd…

Computational Physics · Physics 2024-09-24 Tian Qiu , Joseph E. Subotnik

In this work, two approaches for simulating X-ray absorption (XA) spectra with the complete active space self-consistent field (CASSCF) linear response (LR) method are introduced. The first approach employs the well-known core-valence…

Chemical Physics · Physics 2022-03-10 Benjamin Helmich-Paris

In a recent work, we introduced the foundations of an orthogonally constrained complete active space self-consistent field (OC-CASSCF) framework that produces state-specific molecular orbitals for mutually orthogonal multiconfigurational…

Chemical Physics · Physics 2026-01-28 Loris Delafosse , Vincent Robert , Saad Yalouz

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

A multiscale model based on the coupling of the multiconfigurational self-consistent field (MCSCF) method and the classical atomistic polarizable Fluctuating Charges (FQ) force field is presented. The resulting MCSCF/FQ approach is…

We present the formulation and implementation of the Integral-Screened Configuration-Interaction method (ISCI). The ISCI is a minimal-operational count integral-driven direct Configuration-Interaction (CI) method with a simple and rigorous…

Chemical Physics · Physics 2016-09-27 Lasse Kragh Sørensen , Sebastian Bauch , Lars Bojer Madsen

The recently developed semistochastic heat-bath configuration interaction (SHCI) method is a systematically improvable selected configuration interaction plus perturbation theory method capable of giving essentially exact energies for…

Chemical Physics · Physics 2020-10-01 Yuan Yao , Emmanuel Giner , Junhao Li , Julien Toulouse , C. J. Umrigar