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Density functional theory (DFT) offers a desirable balance between quantitative accuracy and computational efficiency in practical many-electron calculations. Its central component, the exchange-correlation energy functional, has been…

We propose a method that incorporates explicit derivative discontinuity of the total energy with respect to the number of electrons and treats both delocalization and static correlation effects in density functional calculations. Our…

Strongly Correlated Electrons · Physics 2018-03-08 Fei Zhou , Vidvuds Ozolins

The combined density functional theory and multireference configuration interaction (DFT/MRCI) method is a powerful tool for the calculation of excited electronic states of large molecules. There exists, however, a large amount of…

Chemical Physics · Physics 2021-09-27 Simon P. Neville , Michael S. Schuurman

Density matrix embedding theory (DMET) is a fully quantum-mechanical embedding method which shows great promise as a method of defeating the inherent exponential cost scaling of multiconfigurational wave function-based calculations by…

Chemical Physics · Physics 2019-02-07 Matthew R. Hermes , Laura Gagliardi

The density matrix renormalization group (DMRG) method has already proved itself as a very efficient and accurate computational method, which can treat large active spaces and capture the major part of strong correlation. Its application on…

Chemical Physics · Physics 2022-10-31 Pavel Beran , Katarzyna Pernal , Fabijan Pavosevic , Libor Veis

An approximation for the exchange-correlation energy of reduced-density-matrix-functional theory was recently derived from a study of the homogeneous electron gas (N.N. Lathiotakis, N. Helbig, E.K.U. Gross, Phys. Rev. B 75, 195120 (2007)).…

Strongly Correlated Electrons · Physics 2009-11-13 N. N. Lathiotakis , N. Helbig , A. Zacarias , E. K. U. Gross

The on-top pair density [$\Pi(\mathrm{\mathbf{r}})$] is a local quantum-chemical property that reflects the probability of two electrons of any spin to occupy the same position in space. Being the simplest quantity related to the…

Chemical Physics · Physics 2020-12-01 Alberto Fabrizio , Ksenia R. Briling , David D. Girardier , Clemence Corminboeuf

Static correlation is a difficult problem for density-functional theory (DFT) as it arises in cases of degenerate or quasi-degenerate states where a multideterminantal wave function provides the simplest reasonable first approximation to…

Chemical Physics · Physics 2024-01-01 Abraham Ponra , Carolyne Bakasa , Anne Justine Etindele , Mark E. Casida

Multi-configuration range-separated density-functional theory is extended to the time-dependent regime. An exact variational formulation is derived. The approximation, which consists in combining a long-range…

Chemical Physics · Physics 2013-02-27 Emmanuel Fromager , Stefan Knecht , Hans Jørgen Aa. Jensen

A variational formulation for the calculation of interacting fermion systems based on the density-matrix functional theory is presented. Our formalism provides for a natural integration of explicit many-particle effects into standard…

Strongly Correlated Electrons · Physics 2013-05-29 Peter E. Bloechl , Christian F. J. Walther , Thomas Pruschke

The direct variational optimization of the two-electron reduced density matrix (2RDM) can provide a reference-independent description of the electronic structure of many-electron systems that naturally captures strong or nondynamic…

Chemical Physics · Physics 2024-06-19 Run R. Li , Marcus D. Liebenthal , A. Eugene DePrince

We applied renormalized singles (RS) in the multireference density functional theory (DFT) to calculate accurate energies of ground and excited states. The multireference DFT approach determines the total energy of the $N$-electron system…

Chemical Physics · Physics 2022-07-04 Jiachen Li , Zehua Chen , Weitao Yang

A multiconfigurational adiabatic connection (AC) formalism is an attractive approach to computing dynamic correlation within CASSCF and DMRG models. Practical realizations of AC have been based on two approximations: i) fixing one- and…

Chemical Physics · Physics 2023-02-15 Mikuláš Matoušek , Michał Hapka , Libor Veis , Katarzyna Pernal

In [Phys. Rev. Lett. 127, 023001 (2021)] a reduced density matrix functional theory (RDMFT) has been proposed for calculating energies of selected eigenstates of interacting many-fermion systems. Here, we develop a solid foundation for this…

Quantum Physics · Physics 2022-05-06 Julia Liebert , Federico Castillo , Jean-Philippe Labbé , Christian Schilling

The variational determination of the two-fermion reduced density matrix is described for harmonically trapped, ultracold few-fermion systems in one dimension with equal spin populations. This is accomplished by formulating the problem as a…

Quantum Gases · Physics 2022-11-11 Mitchell J. Knight , Harry M. Quiney , Andy M. Martin

Parametric two-electron reduced-density-matrix (p-2RDM) methods have enjoyed much success in recent years; the methods have been shown to exhibit accuracies greater than coupled cluster with single and double substitutions (CCSD) for both…

Chemical Physics · Physics 2010-09-02 A. Eugene DePrince , David A. Mazziotti

Multi-configurational wave-function theory (MC-WFT) that combines complete active space self-consistent field (CASSCF) approach with subsequent state interaction (SI) treatment of spin-orbit coupling (SOC), abbreviated as CASSCF-SO, plays…

Chemical Physics · Physics 2025-03-11 Zhe-Bin Guan , Hong Jiang

The Reduced Density Matrix Functional Theory (RDMFT) is a remarkable tool for studying properties of ground states of strongly interacting quantum many body systems. As it gives access to the one-particle reduced density matrix of the…

Quantum Gases · Physics 2021-10-20 Tomasz Maciążek

The dissociation of $\rm N_2$ and $\rm N_2^+$ has been studied by using the \emph{ab initio} Density Matrix Renormalization Group (DMRG) method. Accurate Potential Energy Surfaces (PES) have been obtained for the electronic ground states of…

Chemical Physics · Physics 2018-02-21 Christian Stemmle , Örs Legeza , Beate Paulus

Stochastic and mixed stochastic-deterministic density functional theory (DFT) are promising new approaches for the calculation of the equation-of-state and transport properties in materials under extreme conditions. In the intermediate warm…

Computational Physics · Physics 2023-09-27 Vidushi Sharma , Lee A. Collins , Alexander J. White