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Rydberg excited states of molecules pose a challenge for electronic structure calculations because of their highly diffuse electron distribution. Even large and elaborate atomic basis sets tend to underrepresent the long-range tail, overly…

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

Calculations of highly excited and delocalized molecular vibrational states are computationally challenging tasks, which strongly depends on the choice of coordinates for describing vibrational motions. We introduce a new method that…

A set of density functionals coming from different rungs on Jacob's ladder are employed to evaluate the electronic excited states of three Ru(II) complexes. While most studies on the performance of density functionals compare the vertical…

The method of analytic continuation is used to find exact integral equations for a selection of finite-volume energy levels for the non-unitary minimal models $M_{2,2N+3}$ perturbed by their $\varphi_{13}$ operators. The N=2 case is studied…

High Energy Physics - Theory · Physics 2009-10-30 Patrick Dorey , Roberto Tateo

The computation of small concise and comprehensible excited state wave functions is needed because many electronic processes occur in excited states. But since the excited energies are saddle points in the Hilbert space of wave functions,…

Chemical Physics · Physics 2016-02-04 Naoum C. Bacalis

We show that, in certain circumstances, exact excitation energies appear as locally site-independent (or flat) modes if one records the excitation spectrum of the effective Hamiltonian while sweeping through the lattice in the variational…

Strongly Correlated Electrons · Physics 2017-08-24 Natalia Chepiga , Frédéric Mila

Typical density functional theory (DFT) and approximations thereto solve the many-electron ground state problem by working from a numerically efficient non-interacting Kohn-Sham reference system; and benefit from useful minimization…

Chemical Physics · Physics 2025-04-02 Tim Gould

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

State-specific approximations can provide an accurate representation of challenging electronic excitations by enabling relaxation of the electron density. While state-specific wave functions are known to be local minima or saddle points of…

Chemical Physics · Physics 2022-01-06 Hugh G. A. Burton

We present an approach for accurate calculation of exchange energy and total energy for excited states using time independent density functional formalism. This is done by inclusion of gradient correction into the excited state exchange…

Chemical Physics · Physics 2012-01-31 Md. Shamim , Manoj K. Harbola

Solving excited states is a challenging task for interacting systems. For one-dimensional critical systems, however, excited states can be directly accessed from the eigenvectors of the local effective Hamiltonian that is constructed from…

Strongly Correlated Electrons · Physics 2026-05-28 Denise Cocchiarella , Mingru Yang , Yueshui Zhang , Mari Carmen Bañuls , Hong-Hao Tu , Yuhan Liu

We present a first principles strategy for developing state-specific density functional approximations for excited states. We first clarify why approaches based on conventional ground state approximations miss density-driven correlations,…

Chemical Physics · Physics 2025-06-09 Tim Gould , Stephen G Dale , Leeor Kronik , Stefano Pittalis

Recent work from our research group has demonstrated that symmetry-projected Hartree--Fock (HF) methods provide a compact representation of molecular ground state wavefunctions based on a superposition of non-orthogonal Slater determinants.…

Chemical Physics · Physics 2015-06-17 Carlos A. Jiménez-Hoyos , R. Rodríguez-Guzmán , Gustavo E. Scuseria

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

This paper describes a method to do ab initio molecular dynamics in electronically excited systems within the random phase approximation (RPA). Using a dynamical variational treatment of the RPA frequency, which corresponds to the…

Condensed Matter · Physics 2009-10-31 Eric R. Bittner , D. S. Kosov

Accurate prediction of adiabatic $0$-$0$ excited-state energies is crucial for modeling molecular photophysical processes. Here, we benchmark computational strategies for evaluating excited-state energies and singlet-triplet gaps obtained…

Chemical Physics · Physics 2026-05-08 Amrita Bera , Atreyee Majumdar , Raghunathan Ramakrishnan

The formalism to calculate excited state properties from the $GW$-Bethe-Salpeter equation (BSE) method is introduced, providing convenient access to excited state absorption, excited state circular dichroism, and excited state optical…

Chemical Physics · Physics 2024-12-25 Paula Himmelsbach , Christof Holzer

Charge-transfer excited states are highly relevant for applications in molecular electronics. However, the accurate calculation of these states in large systems is challenging since wave function methods are prohibitively expensive,…

Chemical Physics · Physics 2025-05-20 Nicola Bogo , Zeyi Zhang , Martin Head-Gordon , Christopher J. Stein

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