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A systematic method for determining correlated wavefunctions of extended systems in the ground and excited states is presented. It allows to fully exploit the power of quantum-chemical programs designed for correlation calculations of…

Other Condensed Matter · Physics 2007-05-23 V. Bezugly

Astrophysical modeling of processes in environments that are not in local thermal equilibrium requires the knowledge of state-to-state rate coefficients of rovibrational transitions in molecular collisions. These rate coefficients can be…

Chemical Physics · Physics 2022-07-13 Taha Selim , Ad van der Avoird , Gerrit C. Groenenboom

We present an extension of our one-body M{\o}ller-Plesset second-order perturbation (OBMP2) method for open-shell systems. We derived the OBMP2 Hamiltonian through the canonical transformation followed by the cumulant approximation to…

Chemical Physics · Physics 2021-10-04 Lan Nguyen Tran

We present algebraic diagrammatic construction theory for simulating spin-orbit coupling and electron correlation in charged electronic states and photoelectron spectra. Our implementation supports Hartree-Fock and multiconfigurational…

Chemical Physics · Physics 2025-05-12 Rajat Majumder , Alexander Yu. Sokolov

We extend first-order multiconfigurational symmetry-adapted perturbation theory, SAPT(MC), [Hapka M. et al. JCTC, 2021, 17], to account for double-exchange effects, where up to two electron pairs are exchanged between interacting monomers.…

Chemical Physics · Physics 2025-04-21 Dominik Cieśliński , Michał Przybytek , Grzegorz Chałasiński , Michał Hapka

We present unrestricted Hartree Fock method coupled with configuration interaction (CI) method (URHF-CI) suitable for the calculation of ground and excited states of large number of electrons localized by complex gate potentials in…

Mesoscale and Nanoscale Physics · Physics 2009-11-11 Ramin M. Abolfath , Pawel Hawrylak

Perturbation theory with respect to the kinetic energy of the heavy component of a two-component quantum system is introduced. An effective Hamiltonian that is accurate to second order in the inverse heavy mass is derived. It contains a new…

Quantum Physics · Physics 2024-06-21 Ryan Requist

Ab initio methods based on the second-order and higher connected moments, or cumulants, of a reference function have seen limited use in the determination of correlation energies of chemical systems throughout the years. Moment-based…

Chemical Physics · Physics 2023-08-25 Brad Ganoe , Martin Head-Gordon

The accurate computation of excited states remains a challenge in electronic structure theory, especially for systems with a ground state that requires a multireference treatment. In this work, we introduce a novel equation-of-motion (EOM)…

Chemical Physics · Physics 2025-05-28 Shuhang Li , Zijun Zhao , Francesco A. Evangelista

We present a formulation of the multiconfigurational (MC) wave function symmetry-adapted perturbation theory (SAPT). The method is applicable to noncovalent interactions between monomers which require a multiconfigurational description, in…

Chemical Physics · Physics 2021-04-15 Michal Hapka , Michal Przybytek , Katarzyna Pernal

Efficiently recovering dynamic correlation in strongly correlated systems without incurring prohibitive computational costs remains a central challenge in quantum chemistry. In this Perspective, we review and benchmark methods capable of…

Chemical Physics · Physics 2026-05-22 Michał Hapka , Aleksandra Tucholska , Katarzyna Pernal

The $\Delta$NO two-electron density matrix (2-RDM) and energy expression are derived from a multideterminantal wave function. The approximate $\Delta$NO 2-RDM is combined with an on-top density functional and a double-counting correction to…

Chemical Physics · Physics 2022-03-14 Ismael A. Elayan , Rishabh Gupta , Joshua W. Hollett

Based on 280 reference vertical transition energies of various natures (singlet, triplet, valence, Rydberg, $n\to\pi^*$, $\pi\to\pi^*$, and double excitations) extracted from the QUEST database, we assess the accuracy of third-order…

Chemical Physics · Physics 2022-07-04 Martial Boggio-Pasqua , Denis Jacquemin , Pierre-François Loos

Electronic resonances are metastable states that can decay by electron loss. They are ubiquitous across various fields of science, such as chemistry, physics, and biology. However, current theoretical and computational models for resonances…

Chemical Physics · Physics 2025-04-15 Yann Damour , Anthony Scemama , Fábris Kossoski , Pierre-François Loos

A hybrid stochastic-deterministic approach for computing the second-order perturbative contribution $E^{(2)}$ within multireference perturbation theory (MRPT) is presented. The idea at the heart of our hybrid scheme --- based on a…

Chemical Physics · Physics 2018-05-31 Yann Garniron , Anthony Scemama , Pierre-François Loos , Michel Caffarel

New ways to treat electron correlation in electronic structure problems are discussed in the context of many-electron theory. The present work focuses primarily on static correlation. In related work, a method for including dynamical…

Chemical Physics · Physics 2018-09-05 Jerry L. Whitten

The $4d \to 3p$ x-ray transitions in Cu- and Ni-like tungsten ions have been studied theoretically. The multiconfiguration Dirac-Hartree-Fock (MCDHF) method and the large-scale relativistic configuration-interaction (CI) method have been…

Atomic Physics · Physics 2024-05-16 Karol Kozioł , Jacek Rzadkiewicz

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

We present second-order molecular cluster perturbation theory (MCPT(2)), a linear scaling methodology to calculate arbitrarily large systems with explicit calculation of individual wavefunctions in a coupled-cluster framework. This new…

Within the lowest-order relativistic approximation ($\sim v^2/c^2$) and to first order in $m_e/M$, the tensorial form of the relativistic corrections of the nuclear recoil Hamiltonian is derived, opening interesting perspectives for…

Atomic Physics · Physics 2015-05-28 E. Gaidamauskas , C. Nazé , P. Rynkun , G. Gaigalas , P. Jönsson , M. Godefroid