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Natural orbital functional theory is considered for systems with one or more unpaired electrons. An extension of the Piris natural orbital functional (PNOF) based on electron pairing approach is presented, specifically, we extend the…

The relative stability of the singlet, triplet, and quintet spin states of Iron(II) porphyrin (FeP) represents a challenging problem for electronic structure methods. While it is currently accepted that the ground state is a triplet,…

Chemical Physics · Physics 2023-01-05 Juan Felipe Huan Lew-Yee , Jorge M. del Campo , Mario Piris

This work deals with the problem of strongly correlated electrons in two-dimensions (2D). We give a reduced density matrix (RDM) based tool through which the ground-state energy is given as a functional of the natural orbitals and their…

Strongly Correlated Electrons · Physics 2020-02-26 Ion Mitxelena , Mario Piris

Excited-state methods within the nuclear--electronic orbital (NEO) framework have the potential to capture vibrational, electronic, and vibronic transitions in a single calculation. In the NEO approach, specified nuclei, typically protons,…

Chemical Physics · Physics 2026-03-16 Jonathan H. Fetherolf , Fabijan Pavošević , Sharon Hammes-Schiffer

We present an extension of the random--phase approximation (RPA) where the RPA phonons are used as building blocks to construct the excited states. In our model, that we call double RPA (DRPA), we include up to two RPA phonons. This is an…

Nuclear Theory · Physics 2016-02-17 D. Gambacurta , F. Catara , M. Grasso , M. Sambataro , M. V. Andrés , E. G. Lanza

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

The one-particle reduced density matrix functional theory in its natural orbital functional (NOF) version is used to study strongly correlated electrons. We show the ability of the Piris NOF 7 (PNOF7) to describe non-dynamic correlation…

Strongly Correlated Electrons · Physics 2020-02-19 Ion Mitxelena , Mario Piris

The current work presents a natural orbital functional (NOF) for electronic systems with any spin value independent of the external potential being considered, that is, a global NOF (GNOF). It is based on a new two-index reconstruction of…

Chemical Physics · Physics 2021-12-07 Mario Piris

In the past decade, natural orbital functional (NOF) approximations have emerged as prominent tools for characterizing electron correlation. Despite their effectiveness, these approaches, which rely on natural orbitals and their associated…

Chemical Physics · Physics 2024-04-19 Ion Mitxelena , Mario Piris

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

We examine to which extent correlated realistic nucleon-nucleon interactions, derived within the Unitary Correlation Operator Method (UCOM), can describe nuclear collective motion in the framework of first-order random-phase approximation…

Nuclear Theory · Physics 2008-11-26 P. Papakonstantinou , R. Roth , N. Paar

The particle-particle random phase approximation (ppRPA) within the hole-hole channel was recently proposed as an efficient tool for computing excitation energies of point defects in solids [J. Phys. Chem. Lett. 2024, 15, 2757-2764]. In…

Chemical Physics · Physics 2024-06-27 Jiachen Li , Yu Jin , Jincheng Yu , Weitao Yang , Tianyu Zhu

The particle-particle random phase approximation (pp-RPA) has been shown to be capable of describing double, Rydberg, and charge transfer excitations, for which the conventional time-dependent density functional theory (TDDFT) might not be…

Computational Physics · Physics 2017-04-26 Jianfeng Lu , Haizhao Yang

The pair coupled cluster doubles (pCCD) method (where the excitation manifold is restricted to electron pairs) has a series of interesting features. Among others, it provides ground-state energies very close to what is obtained with…

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

We combine recent advances in excited state variational principles, fast multi-Slater Jastrow methods, and selective configuration interaction to create multi-Slater Jastrow wave function approximations that are optimized for individual…

Strongly Correlated Electrons · Physics 2019-06-19 Sergio D. Pineda Flores , Eric Neuscamman

This paper describes a method to do ab initio molecular dynamics in electronically excited systems within the random phase approximation (RPA). Using a dynamical variational treatment of the RPA frequency, which corresponds to the…

Condensed Matter · Physics 2009-10-31 Eric R. Bittner , D. S. Kosov

A microscopic formalism is developed that includes the coupling to two particle-hole phonons in the particle-hole propagator by extending the dressed random phase approximation (DRPA) equation for a finite system. The resulting formalism is…

Nuclear Theory · Physics 2016-09-08 C. Barbieri , W. H. Dickhoff

Density functional calculations of Rydberg excited states up to high energy are carried out for several molecules using an approach where the orbitals are variationally optimized by converging on saddle points on the electronic energy…

Rydberg excited states of molecules pose a challenge for electronic structure calculations because of their highly diffuse electron distribution. Even large and elaborate atomic basis sets tend to underrepresent the long-range tail, overly…

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