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We study using the Bethe-Salpeter formalism the excitation energies of the zincbacteriochlorinbacteriochlorin dyad, a paradigmatic photosynthetic complex. In great contrast with standard timedependent density functional theory calculations…

Materials Science · Physics 2015-06-04 I. Duchemin , T. Deutsch , X. Blase

We present a novel {\em ab initio} approach for computing intramolecular charge and energy transfer rates based upon a projection operator scheme that parses out specific internal nuclear motions that accompany the electronic transition.…

Materials Science · Physics 2016-12-22 Xummo Yang , Eric R. Bittner

Semi-empirical quantum mechanical methods traditionally expand the electron density in a minimal, valence-only electron basis set. The minimal-basis approximation causes molecular polarization to be underestimated, and hence intermolecular…

Chemical Physics · Physics 2015-09-30 Anders S. Christensen , Marcus Elstner , Qiang Cui

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 study within the many-body Green's function GW and Bethe-Salpeter formalisms the excitation energies of a paradigmatic model dipeptide, focusing on the four lowest-lying local and charge-transfer excitations. Our GW calculations are…

Materials Science · Physics 2015-06-17 Carina Faber , Paul Boulanger , Ivan Duchemin , Claudio Attaccalite , Xavier Blase

The resonant transfer of energy from the inversion sublevels in NH$_3$ to He atoms in triplet Rydberg states with principal quantum number $n=38$ has been controlled using electric fields below 15 V/cm in intrabeam collisions at…

Chemical Physics · Physics 2020-01-24 K. Gawlas , S. D. Hogan

A semi-quantitative cluster approach is developed to describe the charge transfer (CT) electron-hole excitations in insulating cuprates in a rather wide energy range up to 10- 15 eV. It generalizes the Zhang-Ng (ZN) model of CT excitons by…

Strongly Correlated Electrons · Physics 2016-08-16 A. S. Moskvin , S. -L. Drechsler , R. Hayn , J. Málek

A number of iterative and perturbative approximations to the full equation-of-motion coupled cluster method with single, double, and triple excitations (EOM-CCSDT) are evaluated in the context of calculating the K-edge core-excitation and…

Chemical Physics · Physics 2025-03-26 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

The combination of the many-body Green's function $GW$ approximation and the Bethe-Salpeter equation (BSE) formalism has shown to be a promising alternative to time-dependent density-functional theory (TD-DFT) for computing vertical…

Chemical Physics · Physics 2020-06-05 Pierre-François Loos , Anthony Scemama , Ivan Duchemin , Denis Jacquemin , Xavier Blase

We present the first application to real molecular systems of the recently proposed linear-response theory for the density-based basis-set correction method [J. Chem. Phys. 158, 234107 (2023)]. We apply this approach to accelerate the…

Chemical Physics · Physics 2024-02-27 Diata Traore , Julien Toulouse , Emmanuel Giner

Upon ionization of an atom or a molecule, another electron (or more) can be simultaneously excited. These concurrently generated states are called "satellites" (or shake-up transitions) as they appear in ionization spectra as higher-energy…

Chemical Physics · Physics 2024-06-13 Antoine Marie , Pierre-François Loos

We present a plane-wave basis set implementation of charge constrained density functional molecular dynamics (CDFT-MD) for simulation of electron transfer reactions in condensed phase systems. Following earlier work of Wu et al. Phys. Rev.…

Chemical Physics · Physics 2015-05-13 H. Oberhofer , J. Blumberger

We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum…

Chemical Physics · Physics 2009-11-11 Anatoli A. Milischuk , Dmitry V. Matyushov , Marshall D. Newton

We describe our efforts of the past few years to create a large set of more than 500 highly-accurate vertical excitation energies of various natures ($\pi \to \pi^*$, $n \to \pi^*$, double excitation, Rydberg, singlet, doublet, triplet,…

Energies for the lowest 56 levels, belonging to the 3s$^2$3p, 3s3p$^2$, 3p$^3$, 3s$^2$3d, 3s3p3d, 3s$^2$4$\ell$ and 3s$^2$5$\ell$ configurations of Si II, are calculated using the {\sc grasp} (General-purpose Relativistic Atomic Structure…

Instrumentation and Methods for Astrophysics · Physics 2015-06-19 KM Aggarwal , FP Keenan

We report the core binding energies of K-edge and L-edge transitions in simple semiconducting and insulating solids using periodic equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD). In our all-electron…

Chemical Physics · Physics 2025-08-04 Ethan A. Vo , Timothy C. Berkelbach

We review the Bethe-Salpeter equation (BSE) approach to the calculation of electronic excitation energies of molecular systems. We recall the general Green's function many-theory formalism and give the working equations of the BSE approach…

Chemical Physics · Physics 2013-04-05 Elisa Rebolini , Julien Toulouse , Andreas Savin

By combining extrapolated selected configuration interaction (sCI) energies obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm with the recently proposed short-range…

Chemical Physics · Physics 2020-06-05 Emmanuel Giner , Anthony Scemama , Julien Toulouse , Pierre-François Loos