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We investigate configuration-interaction (CI) calculations on a basis of molecular orbitals generated by preliminary density-functional theory (DFT) calculations. We use this CI/DFT framework to improve the modeling of core-excited states…

Chemical Physics · Physics 2025-09-11 Giorgio Visentin , Francois Mauger

Accurate yet efficient modeling of chemical systems with pronounced static correlation in their excited states remains a significant challenge in quantum chemistry, as most electronic structure methods that can adequately capture static…

Chemical Physics · Physics 2025-03-07 Sylvia J. Bintrim , Kevin Carter-Fenk

Efficient simulation of strongly correlated electrons has become a routine tool in molecular electronic structure theory due to recent advances in approximate configuration interaction (CI) techniques. Nonetheless, the quantitative and…

Quantum Physics · Physics 2026-04-06 Daniel Gibney , Anthony W Schlimgen , Jan-Niklas Boyn

The computationally expensive evaluation and storage of high-rank reduced density matrices (RDMs) has been the bottleneck in the calculation of dynamic correlation for multireference wave functions in large active spaces. We present a…

Chemical Physics · Physics 2020-01-08 Ankit Mahajan , Nick S. Blunt , Iliya Sabzevari , Sandeep Sharma

In this paper, we apply the recently developed ab initio renormalized excitonic method (REM) to the excitation energy calculations of various molecular aggregates, through the extension of REM to the time-dependent density functional theory…

Chemical Physics · Physics 2013-05-07 Yingjin Ma , Haibo Ma

Variational calculations of excited electronic states are carried out by finding saddle points on the surface that describes how the energy of the system varies as a function of the electronic degrees of freedom. This approach has several…

Chemical Physics · Physics 2023-02-15 Yorick L. A. Schmerwitz , Gianluca Levi , Hannes Jónsson

Multireference density functional theory (MR-DFT) provides a pivotal microscopic framework for the description of the ground state properties, low-lying nuclear spectra and transition properties of atomic nuclei. Conventionally, practical…

Nuclear Theory · Physics 2026-05-05 Xin. Zhang , Kouichi. Hagino

State-specific electronic structure theory provides a route towards balanced excited-state wave functions by exploiting higher-energy stationary points of the electronic energy. Multiconfigurational wave function approximations can describe…

Chemical Physics · Physics 2023-07-19 Antoine Marie , Hugh G. A. Burton

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)…

In this chapter we focus first on the theoretical methods and relevant computational approaches to calculate the electronic structure of atoms, molecules, and clusters containing heavy elements for which relativistic effects become…

Chemical Physics · Physics 2021-10-05 Simone Taioli , Stefano Simonucci

Atomistic-to-Continuum (AtC) coupling methods are a novel means of computing the properties of a discrete crystal structure, such as those containing defects, that combine the accuracy of an atomistic (fully discrete) model with the…

Numerical Analysis · Mathematics 2013-09-25 Derek Olson , Pavel Bochev , Mitchell Luskin , Alexander V. Shapeev

The character of an electronically excited state is one of the most important descriptors employed to discuss the photophysics and photochemistry of transition metal complexes. In transition metal complexes, the interaction between the…

Chemical Physics · Physics 2018-02-14 Sebastian Mai , Felix Plasser , Johann Dorn , Maria Fumanal , Chantal Daniel , Leticia González

Multi-configurational approaches yield universal wave function parameterizations that can qualitatively well describe electronic structures along reaction pathways. For quantitative results, multi-reference perturbation theory is required…

Chemical Physics · Physics 2016-09-08 Christopher J. Stein , Vera von Burg , Markus Reiher

Adiabatic quantum computation (AQC), which is particularly useful for combinatorial optimization, becomes more powerful by using excited states, instead of ground states. However, the excited-state AQC is prone to errors due to dissipation.…

Quantum Physics · Physics 2020-12-22 Hayato Goto , Taro Kanao

Accurate spectroscopic investigations of the heaviest elements are inherently challenging, due to their short lifetimes and low production yields. Success of such measurements requires both dedicated experimental techniques and strong…

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

Multi-molecular excited states accompanied by an intra- and inter-molecular geometric relaxation are commonly encountered in optical and electrooptical studies and applications of organic semiconductors as, for example excimers or charge…

Materials Science · Physics 2022-11-14 Sebastian Hammer , Theresa Linderl , Kristofer Tvingstedt , Wolfgang Brütting , Jens Pflaum

The maturation of analytical derivative theory over the past few decades has enabled classical electronic structure theory to provide accurate and efficient predictions of a wide variety of observable properties. However, classical…

Quantum Physics · Physics 2019-06-21 Robert M. Parrish , Edward G. Hohenstein , Peter L. McMahon , Todd J. Martinez

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

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