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An extensive analysis has been carried out of the performance of standard families of basis sets with the hierarchy of coupled cluster methods CC2, CCSD, CC3 and CCSDT in computing selected Oxygen, Carbon and Nitrogen K-edge (vertical) core…

Chemical Physics · Physics 2019-08-13 Johanna P. Carbone , Lan Cheng , Rolf H. Myhre , Devin Matthews , Henrik Koch , Sonia Coriani

Low-scaling electron correlation theory based on the pair natural orbital approximation, PNO-CCSD(T), has become a powerful computational tool. Motivated by the recent discovery of large errors for organometallic molecules, we assess the…

Chemical Physics · Physics 2023-10-10 Reka A. Horvath , Kesha Sorathia , Isabelle Saint , David P. Tew

We report the derivation and implementation of orbital optimization algorithms for the active space decomposition (ASD) model, which are extensions of complete active space self-consistent field (CASSCF) and its occupation-restricted…

Chemical Physics · Physics 2015-08-17 Inkoo Kim , Shane M. Parker , Toru Shiozaki

The strong boundary normalized condition of wavefunction for fully occupied semicore 3d orbitals leads the linear response DFT+U on such metal oxide to have an insurmountable obstacle in Hubbard U determination. We treated the orbital…

Strongly Correlated Electrons · Physics 2015-11-17 Bolong Huang

Traditional multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) methods are based on a single orthonormal orbital basis (OB). For atoms with complicated shell structures, a large OB is needed to saturate all the…

Atomic Physics · Physics 2015-06-12 S. Verdebout , P. Rynkun , P. Jönsson , G. Gaigalas , C. Froese Fischer , M. Godefroid

In contrast to the original Kohn-Sham (KS) formalism, we propose a density functional theory (DFT) with fractional orbital occupations for the study of ground states of many-electron systems, wherein strong static correlation is shown to be…

Chemical Physics · Physics 2015-06-03 Jeng-Da Chai

When the number of strongly correlated electrons becomes larger, the single-reference coupled-cluster (CC) CCSD, CCSDT, etc. hierarchy displays an erratic behavior, while traditional multi-reference approaches may no longer be applicable…

Chemical Physics · Physics 2025-12-12 Ilias Magoulas , Jun Shen , Piotr Piecuch

State-specific orbital optimized approaches are more accurate at predicting core-level spectra than traditional linear-response protocols, but their utility had been restricted on account of the risk of `variational collapse' down to the…

The performance of time-independent, orbital optimized calculations of excited states is assessed with respect to charge transfer excitations in organic molecules in comparison to the linear-response time-dependent density functional theory…

Chemical Physics · Physics 2024-05-22 Elli Selenius , Alec Elías Sigurdarson , Yorick L. A. Schmerwitz , Gianluca Levi

A shape phase transition between stable octupole deformation and octupole vibrations in Th nuclei is analyzed in a microscopic framework based on nuclear density functional theory. The relativistic functional DD-PC1 is used to calculate…

Nuclear Theory · Physics 2014-02-04 K. Nomura , D. Vretenar , B. -N. Lu

Unitary Coupled Cluster (UCC) theory is a promising variational method for electronic structure calculations, especially for strongly correlated systems and quantum computers. However, its practical application is limited by the steep…

Chemical Physics · Physics 2026-02-05 Prateek Vaish , Brenda Rubenstein

A conceptual difficulty in formulating the density functional theory of the fractional quantum Hall effect is that while in the standard approach the Kohn-Sham orbitals are either fully occupied or unoccupied, the physics of the fractional…

Strongly Correlated Electrons · Physics 2017-05-12 Jianyun Zhao , Manisha Thakurathi , Manish Jain , Diptiman Sen , J. K. Jain

Despite the variety of available computational approaches, state-of-the-art methods for calculating excitation energies such as time-dependent density functional theory (TDDFT), are computationally demanding and thus limited to moderate…

Chemical Physics · Physics 2022-03-10 Martina Stella , Kritam Thapa , Luigi Genovese , Laura E. Ratcliff

We present a basis set correction scheme for the coupled-cluster singles and doubles (CCSD) method. The scheme is based on employing frozen natural orbitals (FNOs) and diagrammatically decomposed contributions to the electronic correlation…

Materials Science · Physics 2021-06-18 Andreas Irmler , Alejandro Gallo , Andreas Grüneis

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

We report an update and enhancement of the ACONFL (conformer energies of large alkanes [Ehlert, S.; Grimme, S.; Hansen, A. J. Phys. Chem. A 2022, 126, 3521-3535]) dataset. For the ACONF12 (n-dodecane) subset, we report basis set limit…

Chemical Physics · Physics 2022-11-15 Golokesh Santra , Jan M. L. Martin

Coupled cluster calculations are traditionally performed over Hartree-Fock reference orbitals (HF-CC methodology). However, it has been repeatedly argued in the literature that the use of a Kohn-Sham reference (KS-CC methodology) might…

Chemical Physics · Physics 2025-03-10 Zsolt Benedek , Paula Tímár , Tibor Szilvási , Gergely Barcza

The dipole moment is a crucial molecular property linked to a molecular system's bond polarity and overall electronic structure. To that end, the electronic dipole moment, which results from the electron density of a system, is often used…

Density functional theory offers accurate structure prediction at acceptable computational cost, but commonly used approximations suffer from delocalization error; this results in inaccurate predictions of quantities such as energy band…

Materials Science · Physics 2022-08-17 Aaron Mahler , Jacob Z. Williams , Neil Qiang Su , Weitao Yang

Reliable computational methodologies and basis sets for modeling x-ray spectra are essential for extracting and interpreting electronic and structural information from experimental x-ray spectra. In particular, the trade-off between…

Chemical Physics · Physics 2025-03-26 Alexis A. A. Delgado , Devin A. Matthews