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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

Multiconfiguration pair-density functional theory (MC-PFDT) has previously been applied successfully to carry out ground-state and excited-state calculations. However, because it includes no interaction between electronic states, MC-PDFT…

The accurate description of electron correlation is a central challenge in computational chemistry, with selected configuration interaction (SCI) emerging as a powerful tool to approach the full CI limit. While recent machine learning (ML)…

Chemical Physics · Physics 2026-05-12 Wan Nie , Songwei Liu , Yingying Yu , Zhiwen Wang , and Jun Yang

Designing scalable, noise-tolerant control protocols for multipartite entanglement is a central challenge for quantum technologies, and it naturally calls for \emph{algorithmic} synthesis of interaction parameters rather than handcrafted…

Quantum Physics · Physics 2026-02-10 Duc-Kha Vu , Minh Tam Nguyen , Özgür E. Müstecaplıoğlu , Fatih Ozaydin

We present a method for finding individual excited states' energy stationary points in complete active space self-consistent field theory that is compatible with standard optimization methods and highly effective at overcoming difficulties…

Strongly Correlated Electrons · Physics 2019-04-12 Lan Nguyen Tran , Jacqueline A. R. Shea , Eric Neuscamman

The mean-field solutions of electronic excited states are much less accessible than ground state (e.g.\ Hartree-Fock) solutions. Energy-based optimization methods for excited states, like $\Delta$-scf, tend to fall into the lowest solution…

Chemical Physics · Physics 2022-10-11 Hong-Zhou Ye , Matthew Wellborn , Nathan D. Ricke , Troy Van Voorhis

We introduce single and double particle-hole excitations in the recently revived spin-projected Hartree-Fock. Our motivation is to treat static correlation with spin-projection and recover the residual correlation, mostly dynamic in nature,…

Chemical Physics · Physics 2016-01-20 Takashi Tsuchimochi , Seiichiro Ten-no

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

The similarity transformed equation of motion coupled cluster (STEOM-CC) method is benchmarked against CC3 and EOM-CCSDT-3 for a large test set of valence excited states of organic molecules studied by Schreiber et al. [M. Schreiber, M.R.…

Chemical Physics · Physics 2018-01-09 J. Sous , P. Goel , M. Nooijen

Asymptotics-based configuration-interaction (CI) methods [G. Friesecke and B. D. Goddard, Multiscale Model. Simul. 7, 1876 (2009)] are a class of CI methods for atoms which reproduce, at fixed finite subspace dimension, the exact…

Quantum Physics · Physics 2012-04-06 Christian Mendl , Gero Friesecke

Following our previous work focussing on compounds containing up to 3 non-hydrogen atoms [\emph{J. Chem. Theory Comput.} {\bfseries 14} (2018) 4360--4379], we present here highly-accurate vertical transition energies obtained for 27…

We introduce a new equation-of-motion coupled-cluster method based on a pair coupled-cluster doubles (pCCD) reference, termed frozen-pair EOM-CCSD (EOM-fpCCSD). This approach combines the computational efficiency of the pCCD ansatz with a…

Chemical Physics · Physics 2026-05-06 Katharina Boguslawski , Paweł Tecmer

Intermolecular charge-transfer (xCT) excited states important for various practical applications are challenging for many standard computational methods. It is highly desirable to have an affordable method that can treat xCT states…

Chemical Physics · Physics 2024-11-04 Nhan Tri Tran , Lan Nguyen Tran

The computation of excited electronic states with commonly employed (approximate) methods is challenging, typically yielding states of lower quality than the corresponding ground state for a higher computational cost. In this work, we…

Materials Science · Physics 2020-04-01 Nell Karpinski , Pablo Ramos , Michele Pavanello

Single reference coupled-cluster (CC) methods for electronic excitation are based on a biorthogonal representation (bCC) of the (shifted) Hamiltonian in terms of excited CC states, also referred to as correlated excited (CE) states, and an…

Other Condensed Matter · Physics 2012-08-07 J. Schirmer , F. Mertins

Due to their diverse nature, the faithful description of excited states within electronic structure theory methods remains one of the grand challenges of modern theoretical chemistry. Quantum Monte Carlo (QMC) methods have been applied very…

Chemical Physics · Physics 2020-06-05 Anthony Scemama , Michel Caffarel , Anouar Benali , Denis Jacquemin , Pierre-François Loos

We introduce the multistate iterative qubit coupled cluster (MS-iQCC) method, a quantum-inspired algorithm that runs efficiently on classical hardware and is designed to predict both ground and excited electronic states of molecules.…

Chemical Physics · Physics 2026-01-05 Robert A. Lang , Shashank G. Mehendale , Ilya G. Ryabinkin , Artur F. Izmaylov

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

By correlating only the 1-particle states occupied in the reference determinant the conventional design for the single-reference R12/F12 explicitly-correlated methods biases them towards the ground state description thereby making treatment…

Chemical Physics · Physics 2025-10-13 Conner Masteran , Bimal Gaudel , Edward F. Valeev

Wavefunctions restricted to electron pair states are promising models for strongly-correlated systems. Specifically, the pair Coupled Cluster Doubles (pCCD) ansatz allows us to accurately describe bond dissociation processes and…

Strongly Correlated Electrons · Physics 2019-05-01 Katharina Boguslawski
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