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We present a formulation of excited state mean-field theory in which the derivatives with respect to the wave function parameters needed for wave function optimization (not to be confused with nuclear derivatives) are expressed analytically…

Chemical Physics · Physics 2020-06-24 Luning Zhao , Eric Neuscamman

We present a mean field theory for excited states that is broadly analogous to ground state Hartree-Fock theory. Like Hartree-Fock, our approach is deterministic, state-specific, applies a variational principle to a minimally correlated…

Strongly Correlated Electrons · Physics 2018-08-28 Jacqueline A. R. Shea , Eric Neuscamman

We explore the possibility of calculating electronic excited states by using perturbation theory along a range-separated adiabatic connection. Starting from the energies of a partially interacting Hamiltonian, a first-order correction is…

Chemical Physics · Physics 2014-12-15 Elisa Rebolini , Julien Toulouse , Andrew M. Teale , Trygve Helgaker , Andreas Savin

In quantum chemistry, obtaining a system's mean-field solution and incorporating electron correlation in a post Hartree-Fock (HF) manner comprise one of the standard protocols for ground-state calculations. In principle, this scheme can…

Chemical Physics · Physics 2020-09-02 Hong-Zhou Ye , Troy Van Voorhis

Excited states in molecules can be difficult to investigate and generally require methods that are either computationally expensive or are not universally accurate. Recent research has focused on using higher-energy Slater determinants as…

Chemical Physics · Physics 2023-01-26 Diana-Gabriela Oprea , Hugh G. A. Burton

We present an excited-state-specific coupled-cluster approach in which both the molecular orbitals and cluster amplitudes are optimized for an individual excited state. The theory is formulated via a pseudoprojection of the traditional…

Chemical Physics · Physics 2023-11-27 Harrison Tuckman , Eric Neuscamman

We present the application of the recently developed one-body M{\o}ller--Plesset perturbation theory (OBMP2) to the prediction of K-edge excited states. OBMP2 is a self-consistent perturbation theory in which a canonical transformation…

Chemical Physics · Physics 2026-03-13 Lan Nguyen Tran

We investigate an extension of excited state mean-field theory in which the energy expression is augmented with density functional components in an effort to include the effects of weak electron correlations. The approach remains…

Chemical Physics · Physics 2020-02-05 Luning Zhao , Eric Neuscamman

We investigate the use of perturbation theory in finite sized frustrated spin systems by calculating the effect of quantum fluctuations on coherent states derived from the classical ground state. We first calculate the ground and first…

Strongly Correlated Electrons · Physics 2009-10-31 N. P. Konstantinidis , D. Coffey

The perturbation theory in QED used the new form of ground state as a state of interacted particles is proposed. The mean electromagnetic field of charged elementary particle is calculated. The possibility of elimination the problem with…

Quantum Physics · Physics 2007-05-23 G. M. Filippov

We introduce perturbation and coupled-cluster theories based on a cluster mean-field reference for describing the ground state of strongly-correlated spin systems. In cluster mean-field, the ground state wavefunction is written as a simple…

We develop a cubic scaling approach to excited-state-specific second order perturbation theory in which the completeness of a local correlation treatment is carefully matched between the ground and excited state. With this matching, the…

Chemical Physics · Physics 2025-05-14 Rachel Clune , Eric Neuscamman

We consider two perturbative schemes to calculate excitation energies, each employing the Kohn-Sham Hamiltonian as the unperturbed system. Using accurate exchange-correlation potentials generated from essentially exact densities and their…

Condensed Matter · Physics 2009-10-30 Claudia Filippi , C. J. Umrigar , X. Gonze

We show that by working in a basis similar to that of the natural transition orbitals and using a modified zeroth order Hamiltonian, the cost of a recently-introduced perturbative correction to excited state mean field theory can be reduced…

Chemical Physics · Physics 2020-09-03 Rachel Clune , Jacqueline A. R. Shea , Eric Neuscamman

We show that, as in Hartree Fock theory, the orbitals for excited state mean field theory can be optimized via a self-consistent one-electron equation in which electron-electron repulsion is accounted for through mean field operators. In…

Chemical Physics · Physics 2020-12-02 Tarini S. Hardikar , Eric Neuscamman

A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order M{\o}ller-Plesset partitioning of the Hamiltonian is used to obtain the well known…

Chemical Physics · Physics 2015-07-09 Jason N. Byrd , Varun Rishi , Ajith Perera , Rodney J. Bartlett

Guided by perturbative analysis, we improve the accuracy of Aufbau suppressed coupled cluster theory in simple single excitations, multi-configurational single excitations, and charge transfer excitations while keeping the cost of its…

Chemical Physics · Physics 2025-03-26 Harrison Tuckman , Ziheng Ma , Eric Neuscamman

The potential of mean-field decomposition techniques in interpreting electronic transitions in molecules is explored, particularly, the usefulness of these for offering computational signatures of different classes of such excitations. When…

Chemical Physics · Physics 2022-02-14 Janus J. Eriksen

In this work, we revisited the idea of using the coupled-cluster ground state formalism to target excited states. Our main focus was targeting doubly excited states and double core hole states. Typical equation-of-motion (EOM) approaches…

Chemical Physics · Physics 2019-12-04 Joonho Lee , David W. Small , Martin Head-Gordon

Measurements of energy separations in highly charged ions can in many cases nowadays be performed with very high accuracy, an accuracy that sometimes cannot be matched by the corresponding theoretical calcula- tions. Furthermore, it has…

Atomic Physics · Physics 2013-01-01 Ingvar Lindgren , Sten Salomonson , Johan Holmberg
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