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Using a set of oscillator strengths and excited-state dipole moments of near full configuration interaction (FCI) quality determined for small compounds, we benchmark the performances of several single-reference wave function methods (CC2,…

Chemical Physics · Physics 2021-06-14 Rudraditya Sarkar , Martial Boggio-Pasqua , Pierre-François Loos , Denis Jacquemin

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

The performance of time-independent, orbital optimized calculations of excited states is assessed with respect to charge transfer excitations in organic molecules in comparison to the linear-response time-dependent density functional theory…

Chemical Physics · Physics 2024-05-22 Elli Selenius , Alec Elías Sigurdarson , Yorick L. A. Schmerwitz , Gianluca Levi

Cyclobutadiene is a well-known playground for theoretical chemists and is particularly suitable to test ground- and excited-state methods. Indeed, due to its high spatial symmetry, especially at the $D_{4h}$ square geometry but also in the…

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

Linear response time dependent density functional theory (TDDFT), which builds upon configuration interaction singles (CIS) and TD-Hartree-Fock (TDHF), is the most widely used class of excited state quantum chemistry methods and is often…

Chemical Physics · Physics 2019-10-14 Diptarka Hait , Adam Rettig , Martin Head-Gordon

Self-consistent field theory (SCFT) is one of the most widely-used framework in studying the equilibrium phase behaviors of inhomogenous polymers. For liquid crystalline polymeric systems, the main numerical challenges of solving SCFT…

Numerical Analysis · Mathematics 2024-09-16 Zhijuan He , Kai Jiang , Liwei Tan , Xin Wang

A quantum-field approach for describing many-particle Fermi systems at finite temperatures and with spontaneously broken symmetry has been proposed. A generalized model of self-consistent field (SCF), which allows one to describe the states…

Statistical Mechanics · Physics 2013-03-21 Yu. M. Poluektov

Excited-state absorption (ESA) corresponds to the transition between two electronic excited states and is a fundamental process for probing and understanding light-matter interactions. Accurate modeling of ESA is indeed often required to…

Chemical Physics · Physics 2025-05-26 Jakub Širůček , Boris Le Guennic , Yann Damour , Pierre-François Loos , Denis Jacquemin

Almost all time-dependent density-functional theory (TDDFT) calculations of excited states make use of the adiabatic approximation, which implies a frequency-independent exchange-correlation kernel that limits applications to…

Mesoscale and Nanoscale Physics · Physics 2011-12-08 Miquel Huix-Rotllant , Andrei Ipatov , Angel Rubio , Mark E. Casida

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

We propose a new block localized excitation (BLE) method to directly construct diabatic excited states without the need to first compute the adiabatic states. The new method is capable to keep any electrons, spins, and excitations localized…

Chemical Physics · Physics 2020-01-22 Peng Bao , Qiang Shi , Jiali Gao

We propose a new method of calculating electronically excited states that combines a density functional theory (DFT) based ground state calculation with a linear response treatment that employs approximations used in the time-dependent…

Chemical Physics · Physics 2016-05-11 Robert Rüger , Erik van Lenthe , Thomas Heine , Lucas Visscher

Intermolecular charge-transfer is a highly important process in biology and energy-conversion applications where generated charges need to be transported over several moieties. However, its theoretical description is challenging since the…

Chemical Physics · Physics 2024-05-03 Nicola Bogo , Christopher J. Stein

Dynamical mean-field theory (DMFT) is a non-perturbative technique for the investigation of correlated electron systems. Its combination with the local density approximation (LDA) has recently led to a material-specific computational scheme…

Strongly Correlated Electrons · Physics 2009-11-10 D. Vollhardt , K. Held , G. Keller , R. Bulla , Th. Pruschke , I. A. Nekrasov , V. I. Anisimov

Based on a functional-integral formalism, a generalization of the self-energy-functional theory (SFT) is proposed which is applicable to systems of interacting electrons with disorder. Similar to the pure case without disorder, a…

Strongly Correlated Electrons · Physics 2013-05-29 Michael Potthoff , Matthias Balzer

Density functional theory (DFT) based modeling of electronic excited states is of importance for investigation of the photophysical/photochemical properties and spectroscopic characterization of large systems. The widely used linear…

Chemical Physics · Physics 2021-05-11 Diptarka Hait , Martin Head-Gordon

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

We present a general approach to converge excited state solutions to any quantum chemistry orbital optimization process, without the risk of variational collapse. The resulting Square Gradient Minimization (SGM) approach only requires…

Chemical Physics · Physics 2020-03-11 Diptarka Hait , Martin Head-Gordon

The $\Delta$SCF DFT approach defines the system energy as a function of orbital occupancy. Inspired by Landau Fermi liquid theory, we develop an occupancy extrapolation (OE) method that captures excited-state energies via a Taylor expansion…

Chemical Physics · Physics 2026-03-30 Yichen Fan , Weitao Yang