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Orbital relaxation of the core region is a primary source of error in the computation of core ionization and core excitation energies. Recently, Transition-Potential Coupled Cluster (TP-CC) methods have been used to explicitly treat orbital…

Chemical Physics · Physics 2025-03-17 Alexis A. A. Delgado , Devin A. Matthews

Multiconfiguration Hartree-Fock (MCHF) and multiconfiguration Dirac-Hartree-Fock (MCDHF) calculations are performed for the $2p^{5}~^{2}P^{o}$, $2p^4(^{3}P)3s~^{4}P$, $2p^4(^{3}P)3s~^{2}P$ and $2p^4(^{3}P)3p~^{4}S^o$ states of $^{19}$F~I to…

Atomic Physics · Physics 2018-04-12 Nouria Aourir , Messaoud Nemouchi , Michel Godefroid , Per Jönsson

In this work, we develop a mathematical framework for a Selected Configuration Interaction (SCI) algorithm within a bi-orthogonal basis for transcorrelated (TC) calculations. The bi-orthogonal basis used here serves as the equivalent of the…

Chemical Physics · Physics 2023-06-22 Abdallah Ammar , Anthony Scemama , Emmanuel Giner

The Coupled Cluster (CC) method is used to compute the electronic correlation energy in atoms and molecules and often leads to highly accurate results. However, due to its single-reference nature, standard CC in its projected form fails to…

We investigate configuration-interaction (CI) calculations on a basis of molecular orbitals generated by preliminary density-functional theory (DFT) calculations. We use this CI/DFT framework to improve the modeling of core-excited states…

Chemical Physics · Physics 2025-09-11 Giorgio Visentin , Francois Mauger

Pair atomic density fitting (PADF) is a promising strategy to reduce the scaling with system size of quantum chemical methods for the calculation of the correlation energy like the direct random phase approximation (RPA) or second-order…

Chemical Physics · Physics 2023-03-14 Edoardo Spadetto , Pier Herman Theodoor Philipsen , Arno Förster , Lucas Visscher

We introduce a novel three-body correlation factor that is designed to vanish in the core region around each nucleus and approach a universal two-body correlation factor for valence electrons. The Transcorrelated Hamiltonian is used to…

Chemical Physics · Physics 2023-03-07 Abdallah Ammar , Anthony Scemama , Emmanuel Giner

Wave functions based on electron-pair states provide inexpensive and reliable models to describe quantum many-body problems containing strongly-correlated electrons, given that broken-pair states have been appropriately accounted for by,…

Chemical Physics · Physics 2021-03-17 Artur Nowak , Ors Legeza , Katharina Boguslawski

The problem of orbital relaxation in computational core-hole spectroscopies, including x-ray absorption and x-ray photoionization, has long plagued linear response approaches, including equation-of-motion coupled cluster with singles and…

Chemical Physics · Physics 2025-03-26 Megan E. Simons , Devin A. Matthews

The coupling effects in multiphysics processes are often neglected in designing multiscale methods. The coupling may be described by a non-positive definite operator, which in turn brings significant challenges in multiscale simulations. In…

Numerical Analysis · Mathematics 2024-01-05 Xiaofei Guan , Lijian Jiang , Yajun Wang

Low-lying nuclear states of Sm isotopes are studied in the framework of a collective Hamiltonian based on covariant energy density functional theory. Pairing correlation are treated by both BCS and Bogoliubov methods. It is found that the…

Nuclear Theory · Physics 2015-06-18 J. Xiang , Z. P. Li , J. M. Yao , W. H. Long , P. Ring , J. Meng

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

The series expansion formulae are established for the one- and two-center charge densities over complete orthonormal sets of exponential type orbitals introduced by the author. Three-center overlap integrals of appearing in these relations…

Chemical Physics · Physics 2009-02-04 I. I. Guseinov

Multi-configurational wave functions are known to describe electronic structure across a Born-Oppenheimer surface qualitatively correct. However, for quantitative reaction energies, dynamical correlation originating from the many…

Chemical Physics · Physics 2020-04-16 Christopher J. Stein , Markus Reiher

The strong-coupling perturbation theory (SCPT) for correlated electron systems is extended to the case of full Coulomb interaction. The Coulomb mechanism of the orbital polarization is discussed and attention is paid to the importance of…

Strongly Correlated Electrons · Physics 2007-05-23 I. Sandalov , U. Lundin , O. Eriksson

We present a protocol for computing core-ionisation energies for molecules, which is essential for reproducing X-Ray photoelectron spectroscopy experiments. The electronic structure of both the ground state and the core-ionised states are…

Chemical Physics · Physics 2025-04-18 Niklas Göllmann , Matthew R. Ludwig , Peter Wind , Laura Ratcliff , Luca Frediani

Electron correlation and higher-order relativistic effects are probed in the evaluation of scalar and tensor static electric dipole (E1) polarizabilities ($\alpha_d$) of several even- and odd-parity states in cesium (Cs) using the…

Atomic Physics · Physics 2025-07-08 A. Chakraborty , B. K. Sahoo

Localized orbital coupled cluster theory has recently emerged as an nonempirical alternative to DFT for large systems. Intuitively, one might expect such methods to perform less well for highly delocalized systems. In the present work, we…

Chemical Physics · Physics 2020-10-16 Nitai Sylvetsky , Ambar Banerjee , Mercedes Alonso , Jan M. L. Martin

We investigate pfaffian trial wave functions with singlet and triplet pair orbitals by quantum Monte Carlo methods. We present mathematical identities and the key algebraic properties necessary for efficient evaluation of pfaffians.…

Other Condensed Matter · Physics 2013-05-29 M. Bajdich , L. Mitas , L. K. Wagner , K. E. Schmidt

We report new shell-model calculations of the isospin-symmetry-breaking correction to superallowed nuclear beta decay. The most important improvement is the inclusion of core orbitals, which are demonstrated to have a significant impact on…

Nuclear Theory · Physics 2008-11-26 I. S. Towner , J. C. Hardy