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We extend ground-state density-functional theory to excited states and provide the theoretical formulation for the widely used $\Delta SCF$ method for calculating excited-state energies and densities. As the electron density alone is…

Chemical Physics · Physics 2024-03-08 Weitao Yang , Paul W. Ayers

We present a new stochastic extended Lagrangian solution to charge equilibration that eliminates self-consistent field (SCF) calculations, eliminating the computational bottleneck in solving the many-body solution with standard SCF solvers.…

Computational Physics · Physics 2020-05-22 Songchen Tan , Itai Leven , Dong An , Lin Lin , Teresa Head-Gordon

We reexamine $\Delta$CCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient…

Chemical Physics · Physics 2024-06-13 Yann Damour , Anthony Scemama , Denis Jacquemin , Fábris Kossoski , Pierre-François Loos

An extended first-principles molecular dynamics (FPMD) method based on Kohn-Sham scheme is proposed to elevate the temperature limit of the FPMD method in the calculation of dense plasmas. The extended method treats the wave functions of…

Plasma Physics · Physics 2016-09-08 Shen Zhang , Hongwei Wang , Wei Kang , Ping Zhang , Xian-Tu He

We present a general approach to converge excited state solutions to any quantum chemistry orbital optimization process, without the risk of variational collapse. The resulting Square Gradient Minimization (SGM) approach only requires…

Chemical Physics · Physics 2020-03-11 Diptarka Hait , Martin Head-Gordon

Extended Lagrangian Born-Oppenheimer molecular dynamics [{\em Phys.\ Rev.\ Lett.\ } {\bf 2008}, {\em 100}, 123004] is presented for Hartree-Fock theory, where the extended electronic degrees of freedom are represented by a density matrix,…

Computational Physics · Physics 2020-05-29 Anders M. N. Niklasson

In principle, we should not need the time-dependent extension of density-functional theory (TDDFT) for excitations, and in particular not for Molecular Dynamics (MD) studies: the theorem by Hohenberg and Kohn teaches us that for any…

Strongly Correlated Electrons · Physics 2015-05-27 J. L. Alonso , Alberto Castro , Pablo Echenique , Angel Rubio

We propose an excited-state molecular dynamics simulation method based on variational quantum algorithms at a computational cost comparable to that of ground-state simulations. We utilize the feature that excited states can be obtained as…

Chemical Physics · Physics 2023-03-02 Hirotoshi Hirai

Graph-based linear scaling electronic structure theory for quantum-mechanical molecular dynamics simulations is adapted to the most recent shadow potential formulations of extended Lagrangian Born-Oppenheimer molecular dynamics, including…

Chemical Physics · Physics 2023-03-08 Christian F. A. Negre , Michael E. Wall , Anders M. N. Niklasson

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

This chapter presents the development of a density functional theory (DFT)-based method for accurate, reliable treatment of various resonances in atoms. Many of these are known to be notorious for their strong correlation, proximity to more…

Chemical Physics · Physics 2019-04-19 Amlan K. Roy

State-specific complete active space self-consistent field (SS-CASSCF) theory has emerged as a promising route to accurately predict electronically excited energy surfaces away from molecular equilibria. However, its accuracy and…

Chemical Physics · Physics 2024-02-21 Sandra Saade , Hugh G. A. Burton

With the continuous growth of processing power for scientific computing, first principles Born-Oppenheimer molecular dynamics (MD) simulations are becoming increasingly popular for the study of a wide range of problems in materials science,…

Materials Science · Physics 2015-06-04 Anders M. N. Niklasson , Marc J. Cawkwell

A direct orbital optimization method is presented for density functional calculations of excited electronic states using either a real space grid or a plane wave basis set. The method is variational, provides atomic forces in the excited…

Computational Physics · Physics 2022-11-09 Aleksei V. Ivanov , Gianluca Levi , Elvar Ö. Jónsson , Hannes Jónsson

We present a first principles strategy for developing state-specific density functional approximations for excited states. We first clarify why approaches based on conventional ground state approximations miss density-driven correlations,…

Chemical Physics · Physics 2025-06-09 Tim Gould , Stephen G Dale , Leeor Kronik , Stefano Pittalis

The simulation of molecular electronic structure is an important application of quantum devices. Recently, it has been shown that quantum devices can be effectively combined with classical supercomputing centers in the context of the…

Quantum Physics · Physics 2025-02-28 Stefano Barison , Javier Robledo Moreno , Mario Motta

We present our successful implementation of the quantum electrodynamics coupled-cluster method with single and double excitations (QED-CCSD) for electronic and bosonic amplitudes, covering both individual and mixed excitation processes…

Quantum Physics · Physics 2024-09-12 Himadri Pathak , Nicholas P. Bauman , Ajay Panyala , Karol Kowalski

Electronic excited states are central to a vast array of physical and chemical phenomena, yet accurate and efficient methods for preparing them on quantum devices remain challenging and comparatively underexplored. We introduce a general…

Quantum Physics · Physics 2026-02-02 Hao-En Li , Lin Lin

Building on our recent study [https://doi.org/10.1021/acs.jpclett.3c02052, J. Phys. Chem. Lett. 14, 8780 (2023)], we explore the generalization of the ground-state Kohn-Sham (KS) formalism of density-functional theory (DFT) to the (singlet)…

Chemical Physics · Physics 2025-04-15 Pierre-François Loos , Sara Giarrusso

The extended Lagrangian molecular dynamics (XLMD) method provides a useful framework for reducing the computational cost of a class of molecular dynamics simulations with constrained latent variables. The XLMD method relaxes the constraints…

Numerical Analysis · Mathematics 2020-10-16 Dong An , Lin Lin , Michael Lindsey