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Analytical nuclear gradients for fully internally contracted complete active space second-order perturbation theory (CASPT2) are reported. This implementation has been realized by an automated code generator that can handle spin-free…

Chemical Physics · Physics 2015-02-11 Matthew K. MacLeod , Toru Shiozaki

Analytic gradient routines are a desirable feature for quantum mechanical methods, allowing for efficient determination of equilibrium and transition state structures and several other molecular properties. In this work, we present…

This work presents a novel approach to distribute orbitals into subspaces within electron-pairing-based natural orbital functionals (NOFs). This approach modifies the coupling between weakly and strongly occupied orbitals by applying an…

Chemical Physics · Physics 2025-02-05 Élodie Boutou , Juan Felipe Huan Lew-Yee , Jose Maria Mercero , Mario Piris

The exchange-correlation energy in Kohn-Sham density functional theory is expressed as a functional of the electronic density and the Kohn-Sham orbitals. An alternative to Kohn-Sham theory is to express the energy as a functional of the…

Computational Physics · Physics 2009-10-31 S. Goedecker , C. Umrigar

The energy and analytic gradient are developed for FMO combined with the Hartree-Fock method augmented with three empirical corrections (HF-3c). The auxiliary basis set approach to FMO is extended to perform pair interaction energy…

Chemical Physics · Physics 2018-08-01 Dmitri G. Fedorov , Jimmy C. Kromann , Jan H. Jensen

Selective configuration interaction methods approximate correlated molecular ground- and excited states by considering only the most relevant Slater determinants in the expansion. While a recently proposed neural-network-assisted approach…

The current work presents a new single-reference method for capturing at the same time the static and dynamic electron correlation. The starting-point is a determinant wavefunction formed with natural orbitals obtained from a new…

Chemical Physics · Physics 2017-08-16 Mario Piris

Theory of non-equilibrium Green's function (NGF) provides a practical framework for studying quantum many-body systems out of equilibrium. Extending the previous mean field approach developed for nuclear systems in one dimension with NGF,…

Nuclear Theory · Physics 2020-08-26 Hao Lin , Hossein Mahzoon , Arnau Rios , Pawel Danielewicz

Orbital-free density functional theory as an extension of traditional Thomas-Fermi theory has attracted a lot of interest in the past decade because of developments in both more accurate kinetic energy functionals and highly efficient…

Materials Science · Physics 2009-11-10 Hong Jiang , Weitao Yang

We present a natural orbital-based implementation of the intermediate Hamiltonian Fock space coupled-cluster method for (1,1) sector of Fock space. The use of natural orbital significantly reduces the computational cost and can…

Chemical Physics · Physics 2021-09-07 Soumi Haldar , Achintya Kumar Dutta

The ground state of atoms from H to Ar was calculated using a self-interaction correction to local and gradient dependent density functionals. The correction can significantly improve the total energy and makes the orbital energies…

Atomic and Molecular Clusters · Physics 2013-08-29 Simon Klüpfel , Peter Klüpfel , Hannes Jonsson

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

Occupation numbers of natural orbitals capture the physics of strong electron correlations in momentum space. A Natural Orbital Density Functional Theory based on the antisymmetrized geminal product provides these occupation numbers and the…

Strongly Correlated Electrons · Physics 2014-05-06 B. Barbiellini

We present the theory of analytical Hartree-Fock gradients for periodic systems as implemented in the code CRYSTAL. We demonstrate how derivatives of the integrals can be computed with the McMurchie-Davidson algorithm. Highly accurate…

Materials Science · Physics 2007-05-23 K. Doll , V. R. Saunders , N. M. Harrison

To explore the applicability of orbital-free density functional theory (OF-DFT) in nuclear physics, we perform a systematic benchmark of 36 one-point kinetic energy density functionals, which are originally developed for electron systems in…

Nuclear Theory · Physics 2026-05-20 Tian Shuai Shang , Jian Li , Haozhao Liang , Xinhui Wu , Cheng Ma , Wenhui Mi , Xuecheng Shao , Yanchao Wang

Accurately modeling photochemical reactions is difficult due to the presence of conical intersections and locally avoided crossings as well as the inherently multiconfigurational character of excited states. As such, one needs a multi-state…

Chemical Physics · Physics 2024-04-26 Matthew R. Hennefarth , Matthew R. Hermes , Donald G. Truhlar , Laura Gagliardi

In electronic structure theory, the availability of analytical derivative is one of the desired features for a method to be useful in practical applications, as it allows for geometry optimization as well as computation of molecular…

Chemical Physics · Physics 2017-03-08 Takashi Tsuchimochi , Seiichiro Ten-no

We introduce affordable computational strategies for calculating orbital and pair-orbital energies in atomic and molecular systems. Our methods are based on the pair Coupled Cluster Doubles (pCCD) ansatz and its orbital-optimized variant.…

Chemical Physics · Physics 2025-02-06 Seyedehdelaram Jahani , Somayeh Ahmadkhani , Katharina Boguslawski , Paweł Tecmer

An energy functional for orbital based $O(N)$ calculations is proposed, which depends on a number of non orthogonal, localized orbitals larger than the number of occupied states in the system, and on a parameter, the electronic chemical…

mtrl-th · Physics 2016-09-07 Jeongnim Kim , Francesco Mauri , Giulia Galli

We derive and implement analytic nuclear gradients and derivative couplings for a constrained Complete Active Space Self-Consistent Field with a small active space designed to model electron or hole transfer. Using a Lagrangian formalism,…

Computational Physics · Physics 2025-09-01 Tian Qiu , Joseph E. Subotnik