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This work discusses a protocol for constructing highly accurate potential energy curves (PECs) for the lowest two states of Rb$_{2}^+$, i.e. $X\,{}^2{\Sigma}{_g^+}$ and $(1) {}^2\Sigma{_u^+}$, using an additivity scheme based on…

Atomic Physics · Physics 2022-09-21 Jan Schnabel , Lan Cheng , Andreas Köhn

The accurate calculation of excited state properties of interacting electrons in the condensed phase is an immense challenge in computational physics. Here, we use state-of-the-art equation-of-motion coupled-cluster theory with single and…

Chemical Physics · Physics 2019-07-10 Alan M. Lewis , Timothy C. Berkelbach

Electric quadrupole (E2) and magnetic dipole (M1) transition amplitudes among the low-lying states of quadruply ionized vanadium V$^{4+}$, important in various field of experimental and astrophysics are presented very accurately. Most of…

Atomic Physics · Physics 2009-11-13 Gopal Dixit , B. K. Sahoo , P. C. Deshmukh , R. K. Chaudhuri , Sonjoy Majumder

Due to its favorable computational efficiency time-dependent (TD) density functional theory (DFT) enables the prediction of electronic spectra in a high-throughput manner across chemical space. Its predictions, however, can be quite…

This chapter gives an introduction to qualitative and quantitative topological analyses of molecular electronic transitions. Among the possibilities for qualitatively describing how the electronic structure of a molecule is reorganized upon…

Chemical Physics · Physics 2018-11-27 Thibaud Etienne

Theoretical studies of photochemical processes require a description of the energy surfaces of excited electronic states, especially near degeneracies, where transitions between states are most likely. Systems relevant to photochemical…

In this paper, we evaluate the accuracy of the Hermitian form of the downfolding procedure utilizing the double unitary coupled cluster Ansatz (DUCC) on the H6 and H8 benchmark systems. The computational infrastructure employs the…

Quantum Physics · Physics 2023-05-18 Karol Kowalski , Bo Peng , Nicholas P. Bauman

A size-extensive, converging, black-box, ab initio coupled-cluster ($\Delta$CC) ansatz is introduced that computes the energies and wave functions of stationary states from any degenerate or nondegenerate Slater-determinant references with…

Chemical Physics · Physics 2026-05-15 So Hirata

We recently proposed a novel approach to converging electronic energies equivalent to high-level coupled-cluster (CC) computations by combining the deterministic CC($P$;$Q$) formalism with the stochastic configuration interaction (CI) and…

Chemical Physics · Physics 2021-03-23 J. Emiliano Deustua , Jun Shen , Piotr Piecuch

We present an efficient particle-particle random phase approximation (ppRPA) approach that predicts accurate excitation energies of point defects, including the nitrogen-vacancy (NV$^-$) and the silicon-vacancy (SiV$^0$) centers in diamond…

Chemical Physics · Physics 2024-03-13 Jiachen Li , Yu Jin , Jincheng Yu , Weitao Yang , Tianyu Zhu

Quantum-mechanical methods are widely used for understanding molecular interactions throughout biology, chemistry, and materials science. Quantum diffusion Monte Carlo (DMC) and coupled cluster with single, double, and perturbative triple…

The Coupled Cluster (CC) method is used to compute the electronic correlation energy in atoms and molecules and often leads to highly accurate results. However, due to its single-reference nature, standard CC in its projected form fails to…

Coupled-cluster theory with single, double, and perturbative triple excitations (CCSD(T)) -- often considered the "gold standard" of main-group quantum chemistry -- is inapplicable to three-dimensional metals due to an infrared divergence,…

Materials Science · Physics 2023-03-21 Verena A. Neufeld , Timothy C. Berkelbach

Photon-induced electronic excitations are ubiquitously observed in organic chromophore. In this context, we present a simple, alternative time-independent DFT procedure, for computation of single-particle excitation energies, in particular,…

Chemical Physics · Physics 2021-03-01 Abhisek Ghosal , Tarun Gupta , Kishalay Mahato , Amlan K. Roy

Density functional theory (DFT) is a widespread and effective tool in electronic structure calculations for ground-state electron systems. Its success has prompted exploration into the use of DFT for non-collective excited states. The delta…

Chemical Physics · Physics 2025-08-12 Ethan Pollack , Rohan Maniar , John P. Perdew

A reduced-complexity variant of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) method is formulated in terms of state-averaged excited state pair natural orbitals (PNO) designed to describe manifolds of excited states.…

Chemical Physics · Physics 2020-06-09 Chong Peng , Marjory C. Clement , Edward F. Valeev

We discuss the analytic and diagrammatic structure of ionization potential (IP) and electron affinity (EA) equation-of-motion coupled-cluster (EOM-CC) theory, in order to put it on equal footing with the prevalent $GW$ approximation. The…

Chemical Physics · Physics 2019-04-16 Malte F. Lange , Timothy C. Berkelbach

We present the theoretical framework, implementation, and benchmark results for a reduced-cost relativistic equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method based on state-specific frozen natural spinors (SS-FNS). In…

We use the multiconfiguration Dirac-Hartree-Fock (MCDHF) method combined with the relativistic configuration interaction (RCI) approach (GRASP2K) to provide a consistent set of transition energies and radiative transition data for the lower…

Atomic Physics · Physics 2020-01-08 K. Wang , P. Jönsson , G. Del Zanna , M. Godefroid , Z. B. Chen , C. Y. Chen , J. Yan

Perhaps the simplest first-principles approach to electronic structure is to fit the charge distribution of each orbital pair and use those fits wherever they appear in the entire electron-electron (EE) interaction energy. The charge…

Chemical Physics · Physics 2015-11-10 Brett I Dunlap , Mark C Palenik