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Striving to define very accurate vertical transition energies, we perform both high-level coupled cluster (CC) calculations (up to CCSDTQP) and selected configuration interaction (sCI) calculations (up to several millions of determinants)…

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…

In the realm of photochemistry, the significance of double excitations (also known as doubly-excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions…

Chemical Physics · Physics 2024-07-15 Fábris Kossoski , Martial Boggio-Pasqua , Pierre-François Loos , Denis Jacquemin

We report the first investigation of the performance of EOM-CC4 -- an approximate equation-of-motion coupled-cluster model which includes iterative quadruple excitations -- for vertical excitation energies in molecular systems. By…

Chemical Physics · Physics 2021-06-14 Pierre-François Loos , Devin A. Matthews , Filippo Lipparini , Denis Jacquemin

To enrich and enhance the diversity of the \textsc{quest} database of highly-accurate excitation energies [\href{https://doi.org/10.1002/wcms.1517}{V\'eril \textit{et al.}, \textit{WIREs Comput.~Mol.~Sci.}~\textbf{11}, e1517 (2021)}], we…

In the framework of the computational determination of highly-accurate vertical excitation energies in small organic compounds, we explore the possibilities offered by the equation-of-motion formalism relying on the approximate fourth-order…

To expand the existing QUEST database of accurate vertical transition energies [\href{https://doi.org/10.1002/wcms.1517}{V\'eril et al.~\textit{WIREs Comput.~Mol.~Sci.} \textbf{2021}, \textit{11}, e1517}], we have modeled more than 100…

Chemical Physics · Physics 2024-01-26 Pierre-François Loos , Denis Jacquemin

We reexamine $\Delta$CCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient…

Chemical Physics · Physics 2024-06-13 Yann Damour , Anthony Scemama , Denis Jacquemin , Fábris Kossoski , Pierre-François Loos

In the aim of completing our previous efforts devoted to local and Rydberg transitions in organic compounds, we provide a series of highly-accurate vertical transition energies for intramolecular charge-transfer transitions occurring in…

Chemical Physics · Physics 2021-06-14 Pierre-François Loos , Massimiliano Comin , Xavier Blase , Denis Jacquemin

To expand the QUEST database of highly-accurate vertical transition energies, we consider a series of large organic chromogens ubiquitous in dye chemistry, such as anthraquinone, azobenzene, BODIPY, and naphthalimide. We compute, at the CC3…

We investigate the use of orbital-optimized references in conjunction with single-reference coupled-cluster theory with single and double substitutions (CCSD) for the study of core excitations and ionizations of 18 small organic molecules,…

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…

Similarity transformed equation-of-motion coupled cluster theory (STEOM-CC) is an alternative approach to equation-of-motion coupled cluster theory for excited states (EOMEE-CC) which uses a second similarity transformation of the…

Chemical Physics · Physics 2025-03-26 Megan Simons , Devin A. Matthews

The accurate description of doubly-excited states using conventional electronic structure methods is remarkably challenging, primarily because such excited states require the inclusion of doubly or higher excited configurations or the…

Chemical Physics · Physics 2019-05-01 Katharina Boguslawski

We report theoretical best estimates of vertical transition energies (VTEs) for a large number of excited states and molecules: the \textsc{quest} database. This database includes 1489 \emph{aug}-cc-pVTZ VTEs (731 singlets, 233 doublets,…

In single-reference coupled-cluster (CC) methods, one has to solve a set of non-linear polynomial equations in order to determine the so-called amplitudes which are then used to compute the energy and other properties. Although it is of…

Chemical Physics · Physics 2021-09-10 Antoine Marie , Fábris Kossoski , Pierre-François Loos

We scrutinize the performance of different variants of equation of motion coupled cluster (EOM-CC) methods to predict electronic excitation energies and excited state potential energy surfaces in closed-shell actinide species. We focus our…

Chemical Physics · Physics 2020-02-26 Artur Nowak , Paweł Tecmer , Katharina Boguslawski

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

This work presents a series of highly-accurate excited-state properties obtained using high-order coupled-cluster (CC) calculations performed with a series of diffuse containing basis sets, as well as extensive comparisons with experimental…

Chemical Physics · Physics 2021-06-14 Amara Chrayteh , Aymeric Blondel , Pierre-François Loos , Denis Jacquemin

The accurate computation of excited states remains a challenge in electronic structure theory, especially for systems with a ground state that requires a multireference treatment. In this work, we introduce a novel equation-of-motion (EOM)…

Chemical Physics · Physics 2025-05-28 Shuhang Li , Zijun Zhao , Francesco A. Evangelista
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