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The development of variational density functional theory approaches to excited electronic states is impeded by limitations of the commonly used self-consistent field (SCF) procedure. A method based on a direct optimization approach as well…

Chemical Physics · Physics 2022-11-09 Gianluca Levi , Aleksei V. Ivanov , Hannes Jónsson

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

An electrodynamical coupled cluster (CC) methodology starting from a covariant formalism and an equal time approximation, and finally based on the Dirac-Fock picture of the electron and positron fields and Coulomb gauge, is given here. The…

Atomic Physics · Physics 2019-04-30 Sambhu N. Datta

We propose an algorithm for low Mach number reacting flows subjected to electric field that includes the chemical production and transport of charged species. This work is an extension of a multi-implicit spectral deferred correction…

Fluid Dynamics · Physics 2020-06-24 Lucas Esclapez , Valentina Ricchiuti , John B. Bell , Marcus S. Day

Recent trends of ab initio studies and progress in methodologies for electronic structure calculations of strongly correlated electron systems are discussed. The interest for developing efficient methods is motivated by recent discoveries…

Strongly Correlated Electrons · Physics 2010-12-06 Masatoshi Imada , Takashi Miyake

The electronic structure of the ICl+ molecular ion is investigated by using high-level multireference configuration interaction (MRCI) method. To improve computational accuracy, Davidson corrections, spin-orbit coupling (SOC), and…

Atomic Physics · Physics 2025-11-25 Rui Li , Ronglong Dou , Ting Gao , Qinan Li , Chaoqun Song

In this study, two different simple and intuitive semiempirical schemes for computing approximate non-adiabatic coupling vectors (NACVs) between the ground and excited electronic states are presented. The first approximation makes use of…

Chemical Physics · Physics 2019-08-02 Alexander Humeniuk , Roland Mitrić

Fully explicit stabilized multirate (mRKC) methods are well-suited for the numerical solution of large multiscale systems of stiff ordinary differential equations thanks to their improved stability properties. To demonstrate their…

Numerical Analysis · Mathematics 2024-06-25 Giacomo Rosilho de Souza , Marcus J. Grote , Simone Pezzuto , Rolf Krause

To calculate excited states in quantum many-body systems, multi-configuration mixing has often been employed. However, it has been still unclear how to choose important Slater determinants from a huge model space. We propose a novel…

Nuclear Theory · Physics 2022-03-02 Takatoshi Ichikawa , Naoyuki Itagaki

The Alternating Direction Method of Multipliers (ADMM) has gained a lot of attention for solving large-scale and objective-separable constrained optimization. However, the two-block variable structure of the ADMM still limits the practical…

Optimization and Control · Mathematics 2020-03-24 Kresimir Mihic , Mingxi Zhu , Yinyu Ye

Accurate prediction of adiabatic $0$-$0$ excited-state energies is crucial for modeling molecular photophysical processes. Here, we benchmark computational strategies for evaluating excited-state energies and singlet-triplet gaps obtained…

Chemical Physics · Physics 2026-05-08 Amrita Bera , Atreyee Majumdar , Raghunathan Ramakrishnan

Charge-transfer excited states are highly relevant for applications in molecular electronics. However, the accurate calculation of these states in large systems is challenging since wave function methods are prohibitively expensive,…

Chemical Physics · Physics 2025-05-20 Nicola Bogo , Zeyi Zhang , Martin Head-Gordon , Christopher J. Stein

Aligning theoretical atomistic structural models of materials with available experimental data presents a significant challenge for disordered systems. The configurational space to navigate is vast, and faithful realizations require large…

Materials Science · Physics 2025-09-29 Tigany Zarrouk , Miguel A. Caro

We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral…

Statistical Mechanics · Physics 2014-03-05 Artur R. Menzeleev , Franziska Bell , Thomas F. Miller

The symmetry-projected Hartree--Fock ansatz for the electronic structure problem can efficiently account for static correlation in molecules, yet it is often unable to describe dynamic correlation in a balanced manner. Here, we consider a…

Strongly Correlated Electrons · Physics 2015-06-17 Carlos A. Jiménez-Hoyos , R. Rodríguez-Guzmán , Gustavo E. Scuseria

Roles of electron correlation effects in the determination of attachment energies, magnetic dipole hyperfine structure constants and electric dipole (E1) matrix elements of the low-lying states in the singly charged cadmium ion (Cd$^+$)…

Atomic Physics · Physics 2018-03-14 Cheng-Bin Li , Yan-Mei Yu , B. K. Sahoo

Quantum embedding methods have recently developed significantly to model large molecular structures. This work proposes a novel wave function theory in density functional theory (WTF-in-DFT) embedding scheme based on pair-coupled cluster…

Chemical Physics · Physics 2024-01-10 Rahul Chakraborty , Katharina Boguslawski , Paweł Tecmer

Spectroscopic properties of molecules holds great importance for the description of the molecular response under the effect of an UV/Vis electromagnetic radiation. Computationally expensive ab initio (e.g. MultiConfigurational SCF, Coupled…

We introduce state-averaging into the method of Monte Carlo configuration interaction (SA-MCCI) to allow the stable and efficient calculation of excited states. We show that excited potential curves for H$_{3}$, including a crossing with…

Chemical Physics · Physics 2014-03-03 J. P. Coe , M. J. Paterson

Data-driven techniques are increasingly used to replace electronic-structure calculations of matter. In this context, a relevant question is whether machine learning (ML) should be applied directly to predict the desired properties or be…