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A method for increasing the accuracy of configuration interaction (CI) calculations of molecules and other electronic systems is proposed. The energy defect of a given calculation is associated with the electron pair origin of…

Chemical Physics · Physics 2025-11-18 Jerry L. Whitten

We report an efficient implementation of a second-order multireference perturbation theory based on the driven similarity renormalization group (DSRG-MRPT2) [C. Li and F. A. Evangelista, J. Chem. Theory Comput. 11, 2097 (2015)]. Our…

Chemical Physics · Physics 2016-06-22 Kevin P. Hannon , Chenyang Li , Francesco A. Evangelista

We present the first single-reference calculations of the atomic axial tensors (AATs) using wave-function-based methods including dynamic electron correlation effects using second-order M{\o}ller-Plesset perturbation theory (MP2) and…

Chemical Physics · Physics 2024-06-11 Brendan M. Shumberger , T. Daniel Crawford

We present an implementation and benchmark of new approximations in multireference algebraic diagrammatic construction theory for simulations of neutral electronic excitations and UV/Vis spectra of strongly correlated molecular systems…

Chemical Physics · Physics 2021-12-02 Ilia M. Mazin , Alexander Yu. Sokolov

Many-body perturbation theory (MBPT) based on Green's functions and Feynman diagrams provides a fundamental theoretical framework for various \emph{ab initio} computational approaches in molecular and materials science, including the random…

Quantum Physics · Physics 2025-03-20 Yuqi Wang , Wei-Hai Fang , Zhendong Li

Aims. This work reports radiative transition rates and electron impact excitation collision strengths for levels of the 3s23p, 3s3p2, 3s24s, and 3s23d configurations of Siii. Methods. The radiative data were computed using the…

Astrophysics of Galaxies · Physics 2015-05-14 M. A. Bautista , P. Quinet , P. Palmeri , N. R. Badnell , J. Dunn , N. Arav

Present atomic theory provides accurate and reliable results for atoms with a small number of valence electrons. However, most current methods of calculations fail when the number of valence electrons exceeds four or five. This means that…

Atomic Physics · Physics 2024-07-10 M. G. Kozlov , I. I. Tupitsyn , A. I. Bondarev , D. V. Mironova

UGA-SSMRPT2, the spin-free perturbative analogue of Mukerjee's State-Specific Multireference Coupled Cluster Theory (MkMRCC) is known to be successful for size-extensive and intruder-free construction of dissociation curves. This work…

Chemical Physics · Physics 2026-02-05 Shamik Chanda , Pratyush Bhattacharjya , Avijit Sen , Sangita Sen

We present an efficient method of inclusion of the core-valence correlations into the configuration interaction (CI) calculations. These correlations take place in the core area where the potential of external electrons is approximately…

Atomic Physics · Physics 2009-11-13 V. A. Dzuba , V. V. Flambaum

The symmetry-projected Hartree--Fock ansatz for the electronic structure problem can efficiently account for static correlation in molecules, yet it is often unable to describe dynamic correlation in a balanced manner. Here, we consider a…

Strongly Correlated Electrons · Physics 2015-06-17 Carlos A. Jiménez-Hoyos , R. Rodríguez-Guzmán , Gustavo E. Scuseria

The configuration interaction relativistic Hartree-Fock (CI-RHF) model is developed in this work. Compared to the conventional configuration interaction shell model (CISM), the CI-RHF model can be applied to study the structural properties…

Nuclear Theory · Physics 2025-04-14 Jia Liu , Yi Fei Niu , Wen Hui Long

Here is presented an original program based on molecular Schrodinger equations. It is dedicated to target specific states of infrared vibrational spectrum in a very precise way with a minimal usage of memory. An eigensolver combined with a…

Computational Physics · Physics 2018-07-26 Romain Garnier

In this chapter we focus first on the theoretical methods and relevant computational approaches to calculate the electronic structure of atoms, molecules, and clusters containing heavy elements for which relativistic effects become…

Chemical Physics · Physics 2021-10-05 Simone Taioli , Stefano Simonucci

A relativistic coupled-cluster (RCC) theory is implemented to study electron impact excitations of atomic species. As a test case, the electron impact excitations of the $3s ~ ^2S_{1/2} - 3p ~ ^2P_{1/2;3/2}$ resonance transitions are…

Atomic Physics · Physics 2018-02-14 L. Sharma , B. K. Sahoo , P. Malkar , R. Srivastava

Hydrogen tunneling is an important process that impacts reaction rates and molecular spectra. Describing and understanding this process requires a quantum mechanical treatment of the transferring hydrogen. The nuclear-electronic orbital…

Chemical Physics · Physics 2025-07-14 Rachel J. Stein , Christopher L. Malbon , Sharon Hammes-Schiffer

Level energies, wavelengths, electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole transition rates, oscillator strengths, and line strengths from combined relativistic configuration interaction and many-body…

Following our previous work focussing on compounds containing up to 3 non-hydrogen atoms [\emph{J. Chem. Theory Comput.} {\bfseries 14} (2018) 4360--4379], we present here highly-accurate vertical transition energies obtained for 27…

In this work we demonstrate that the heat bath configuration interaction (HCI) and its semistochastic extension can be used to treat relativistic effects and electron correlation on an equal footing in large active spaces to calculate the…

Chemical Physics · Physics 2018-11-08 Bastien Mussard , Sandeep Sharma

With a transcorrelated Hamiltonian, we perform a many body perturbation (MBPT) calculation on the uniform electron gas in the high density regime. By using a correlation factor optimised for a single determinant Jastrow ansatz, the second…

Computational Physics · Physics 2024-06-19 Hongjun Luo , Ali Alavi

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
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