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Accurate prediction of molecular g-tensors for open-shell systems requires a balanced treatment of multireference electron correlation and relativistic spin-orbit coupling. Here, we develop and benchmark spin-orbit quasidegenerate…

Chemical Physics · Physics 2026-04-14 Nicholas Yiching Chiang , Rajat Majumder , Alexander Yu. Sokolov

We extend our recently-developed heat-bath configuration interaction (HCI) algorithm, and our semistochastic algorithm for performing multireference perturbation theory, to the calculation of excited-state wavefunctions and energies. We…

Strongly Correlated Electrons · Physics 2017-11-22 Adam A. Holmes , C. J. Umrigar , Sandeep Sharma

A global hybrid extension of variational two-electron reduced-density matrix (v2RDM)-driven multiconfiguration pair-density functional theory (MCPDFT) is developed. Using a linear decomposition of the electron-electron repulsion term, a…

Chemical Physics · Physics 2019-11-27 Mohammad Mostafanejad , Marcus Dante Liebenthal , A. Eugene DePrince

We analyze a model problem representing a multi-electronic molecule sitting on a metal surface. Working with a reduced configuration interaction Hamiltonian, we show that one can extract very accurate ground state wavefunctions as compared…

Chemical Physics · Physics 2020-09-24 Junhan Chen , Zuxin Jin , Wenjie Dou , Joseph Subotnik

The triplet contribution is computed to the 1 and 2 $^1S^\text{e}_0$ states of the He atom, to the $1\ ^1S^\text{e}_0$ state of the Li$^+$ and Be${^{2+}}$ ions, and to the $X\ ^1\Sigma_\text{g}^+$ ground state of the H$_2$ molecule by…

Atomic Physics · Physics 2023-01-25 Péter Jeszenszki , Edit Mátyus

Inelastic low-energy (0--1 eV) collisions of electrons with HeH$^+$ cations are treated theoretically, with a focus on the rovibrational excitation and dissociative recombination (DR) channels. In an application of {\it ab initio}…

Chemical Physics · Physics 2017-10-30 Roman Čurík , Chris H. Greene

The relativistic approach to electroweak properties of two-particle composite systems developed in previous work is generalized here to the case of nonzero spin. This approach is based on the use of the instant form of relativistic…

High Energy Physics - Phenomenology · Physics 2013-05-29 A. F. Krutov , V. E. Troitsky

We present a relativistic time-dependent density functional theory (TDDFT) approach for the simulation of resonant inelastic X-ray scattering (RIXS) spectra, based on both a full four-component (4c) Dirac-Coulomb Hamiltonian and a modern…

Chemical Physics · Physics 2026-04-17 Lukas Konecny , Muhammed A. Dada , Daniel R. Nascimento , Michal Repisky

We present a method for calculation of the second-order exchange-dispersion energy in the framework of the symmetry-adapted perturbation theory (SAPT) for weakly interacting monomers described with multiconfigurational wave functions. The…

Chemical Physics · Physics 2019-10-11 Hapka Michał , Przybytek Michał , Pernal Katarzyna

First principle theoretical modeling of out-of-equilibrium processes observed in attosecond pump-probe transient absorption spectroscopy (TAS) triggering pure electron dynamics remains a challenging task, specially for heavy elements and/or…

Chemical Physics · Physics 2023-02-14 Torsha Moitra , Lukas Konecny , Marius Kadek , Angel Rubio , Michal Repisky

Leveraging matrix sparsity has proven a fruitful strategy for accelerating quantum chemical calculations. Here we present the hierarchical SOS-MP2 algorithm, which uses hierarchical matrix ($\mathcal{H}^{2}$) compression of the electron…

Chemical Physics · Physics 2025-06-23 Hongji Gao , Xiangmin Jiao , Benjamin G. Levine

Heavy atom compounds represent a challenge for computational chemistry, due to the need for simultaneous treatment of relativistic and correlation effects. Often such systems exhibit also strong correlation which hampers the application of…

Chemical Physics · Physics 2025-02-10 Jakub Višňák , Jan Brandejs , Mihály Máté , Lucas Visscher , Örs Legeza , Jiří Pittner

We present the theory and implementation of a highly efficient relativistic third-order algebraic diagrammatic construction [ADC(3)] method based on a four-component (4c) Dirac-Coulomb (DC) Hamiltonian for the calculation of ionization…

Chemical Physics · Physics 2024-11-01 Sudipta Chakraborty , Tamoghna Mukhopadhyay , Malaya K. Nayak , Achintya Kumar Dutta

An adaptation of the full configuration interaction quantum Monte Carlo (FCIQMC) method is presented, for correlated electron problems containing heavy elements and the presence of significant relativistic effects. The modified algorithm…

Chemical Physics · Physics 2020-10-26 Robert J. Anderson , George H. Booth

We present the implementation of quadratic response theory based upon the relativistic equation-of-motion coupled cluster method. We showcase our implementation, whose generality allows us to consider both time-dependent and…

Chemical Physics · Physics 2024-01-29 Xiang Yuan , Loic Halbert , Lucas Visscher , Andre Severo Pereira Gomes

We numerically examine divergences of the total energy in metallic systems of approximate many-body theories using Hartree--Fock as a reference, including perturbative (M\oller-Plesset, MP), coupled cluster (CC) and configuration…

Chemical Physics · Physics 2012-08-31 James J. Shepherd , Andreas Grüneis

A theoretical framework is presented for the computation of rovibrational polaritonic states of a molecule in a lossless infrared (IR) microcavity. In the proposed approach the quantum treatment of the rotational and vibrational motion of…

Chemical Physics · Physics 2023-10-30 Tamás Szidarovszky

We present systematic relativistic many-body calculations of multipole transition properties for singly charged aluminum ion (Al II) using a method that combines the configuration interaction and many-body perturbation theory (CI+MBPT). Our…

Atomic Physics · Physics 2025-02-25 Yuan-Fei Wei , Zhi-Ming Tang , Xue-Ren Huang , Ming-Lu Bu , Xin-Ye Xu , Yi-Yu Cai

Multi-configurational electronic structure theory delivers the most versatile approximations to many-electron wavefunctions, flexible enough to deal with all sorts of transformations, ranging from electronic excitations, to open-shell…

Chemical Physics · Physics 2024-05-07 Kalman Szenes , Maximilian Moerchen , Paul Fischill , Markus Reiher

A new method for solving the time-dependent two-center Dirac equation is developed. The time-dependent Dirac wave function is represented as a sum of atomic-like Dirac-Sturm orbitals, localized at the ions. The atomic orbitals are obtained…