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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

Understanding the process of molecular photoexcitation is crucial in various fields, including drug development, materials science, photovoltaics, and more. The electronic vertical excitation energy is a critical property, for example in…

Chemical Physics · Physics 2025-03-26 Tingting Zhao , Devin A. Matthews

In the molecular quantum chemistry community, coupled-cluster (CC) methods are well-recognized for their systematic convergence and reliability. The extension of the theory to extended systems has been comparably recent, so that…

Chemical Physics · Physics 2024-10-31 Andreas Grüneis , Evgeny Moerman , Matthias Scheffler , Tonghao Shen , Igor Ying Zhang

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 provide an overview of the successive steps that made possible to obtain increasingly accurate excitation energies with computational chemistry tools, eventually leading to chemically accurate vertical transition energies for small- and…

Chemical Physics · Physics 2020-06-05 Pierre-François Loos , Anthony Scemama , Denis Jacquemin

We report the implementation of equation-of-motion coupled-cluster (EOMCC) method in the four-component relativistic framework with the spherical atomic potential to generate the excited states from a closed-shell atomic configuration. This…

Atomic Physics · Physics 2015-06-19 D. K. Nandy , Yashpal Singh , B. K. Sahoo

Aiming at completing the sets of FCI-quality transition energies that we recently developed (\textit{J.~Chem.~Theory Comput.} \textbf{14} (2018) 4360--4379, \textit{ibid.}~\textbf{15} (2019) 1939--1956, and \textit{ibid.}~\textbf{16} (2020)…

Chemical Physics · Physics 2020-06-18 Pierre-François Loos , Anthony Scemama , Martial Boggio-Pasqua , Denis Jacquemin

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 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

The phenomenon of orbital relaxation upon excitation of core electrons is a major problem in the linear-response treatment of core-hole spectroscopies. Rather than addressing relaxation through direct dynamical correlation of the excited…

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

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

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

Using a series of increasingly refined wavefunction methods able to tackle electronic excited states, namely ADC(2), CC2, CCSD, CCSDR(3) and CC3, we investigate the interplay between geometries and 0-0 energies. We show that, due to a…

Chemical Physics · Physics 2019-05-06 Pierre-François Loos , Denis Jacquemin

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 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

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

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

Basis set convergence of correlation effects on molecular atomization energies beyond the CCSD (coupled cluster with singles and doubles) approximation has been studied near the one-particle basis set limit. Quasiperturbative connected…

Chemical Physics · Physics 2008-08-17 Amir Karton , Peter R. Taylor , Jan M. L. Martin

We report the implementation of 4-component spinor relativistic equation-of-motion coupledcluster method within the single- and double- excitation approximation to calculate ionization potential (EOM-CCSD) of molecules. We have applied this…

Chemical Physics · Physics 2015-02-25 Himadri Pathak , Sudip Sasmal , Malaya K. Nayak , Nayana Vaval , Sourav Pal

In this article, we present new results of high-order coupled cluster method (CCM) calculations, based on a N\'eel model state with spins aligned in the $z$-direction, for both the ground- and excited-state properties of the spin-half {\it…

Strongly Correlated Electrons · Physics 2013-05-30 R. F. Bishop , D. J. J. Farnell , S. E. Krueger , J. B. Parkinson , J. Richter , C. Zeng