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We have implemented noniterative triples corrections to the energy from coupled-cluster with single and double excitations (CCSD) within the 1-electron exact two-component (1eX2C) relativistic framework. The effectiveness of both the…

Fragmentation methods applied to multireference wave functions constitute a road towards the application of highly accurate ab initio wave function calculations to large molecules and solids. However, it is important for reproducibility and…

Chemical Physics · Physics 2020-07-23 Matthew R. Hermes , Laura Gagliardi

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 show that the spin-and-space unrestricted Hartree-Fock method, in conjunction with the companion step of the restoration of spin and space symmetries via Projection Techniques (when such symmetries are broken), is able to describe the…

Mesoscale and Nanoscale Physics · Physics 2009-11-07 Constantine Yannouleas , Uzi Landman

We use the recently-developed Heat-bath Configuration Interaction (HCI) algorithm as an efficient active-space solver to perform multi-configuration self-consistent field calculations (HCISCF) with large active spaces. We give a detailed…

Chemical Physics · Physics 2018-11-08 James E. T. Smith , Adam A. Holmes , Bastien Mussard , Sandeep Sharma

The near-exact iCIPT2 approach for strongly correlated systems of electrons, which stems from the combination of iterative configuration interaction (iCI, an exact solver of full CI) with configuration selection for static correlation and…

Chemical Physics · Physics 2022-04-13 Ning Zhang , Yunlong Xiao , Wenjian Liu

An eight-component formalism is proposed for the relativistic two-fermion problem. In QED, it extends the applicability of the Dirac equation with hyperfine interaction to the positronium case. The use of exact relativistic two-body…

High Energy Physics - Phenomenology · Physics 2009-10-31 Ruth Haeckl , Viktor Hund , Hartmut Pilkuhn

Complete active space self-consistent field (CASSCF) computations can be realized at polynomial cost via the variational optimization of the active-space two-electron reduced-density matrix (2-RDM). Like conventional approaches to CASSCF,…

Chemical Physics · Physics 2018-12-10 Mohammad Mostafanejad , A. Eugene DePrince

Core-level spectra of 1s electrons of elements heavier than Ne show significant relativistic effects. We combine advances in orbital optimized DFT (OO-DFT) with the spin-free exact two-component (X2C) model for scalar relativistic effects,…

Chemical Physics · Physics 2022-04-19 Leonardo A. Cunha , Diptarka Hait , Richard Kang , Yuezhi Mao , Martin Head-Gordon

X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due…

We report internally contracted relativistic multireference configuration interaction (ic-MRCI), complete active space second-order perturbation (CASPT2), and strongly contracted n-electron valence state perturbation theory (NEVPT2) on the…

Chemical Physics · Physics 2015-12-31 Toru Shiozaki , Wataru Mizukami

Multireference systems are usually challenging to investigate using ab initio methods as they require an accurate description of static electron correlation. The urgency of developing similar approaches is even more pressing when molecules…

Chemical Physics · Physics 2025-06-11 Riccardo Alessandro , Matteo Castagnola , Henrik Koch , Enrico Ronca

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

L-edge X-ray absorption spectra for first-row transition metal complexes are obtained from relativistic equation-of-motion singles and doubles coupled-cluster (EOM-CCSD) calculations that make use of the core-valence separation (CVS)…

The recently developed localized orbital scaling correction (LOSC) method shows the ability to systematically and size-consistently reduce the delocalization error existing in conventional density functional approximations (DFAs). Applying…

Chemical Physics · Physics 2020-10-19 Yuncai Mei , Zehua Chen , Weitao Yang

An active space variational calculation of the 2-electron reduced density matrix (2-RDM) is derived and implemented where the active orbitals are correlated within the pair approximation. The pair approximation considers only doubly…

Chemical Physics · Physics 2020-10-13 Kade Head-Marsden , David A. Mazziotti

In this work, we investigate the possibility of improving multireference-driven coupled cluster (CC) approaches with an algorithm that iteratively combines complete active space (CAS) calculations with tailored CC and externally corrected…

Chemical Physics · Physics 2025-03-06 Robin Feldmann , Max Mörchen , Jakub Lang , Michał Lesiuk , Markus Reiher

A two-parameter extension of the density-scaled double hybrid approach of Sharkas et al. [J. Chem. Phys. 134, 064113 (2011)] is presented. It is based on the explicit treatment of a fraction of multideterminantal exact exchange. The…

Chemical Physics · Physics 2012-01-12 Emmanuel Fromager

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

It is shown that the 2 X 2 matrix Hamiltonian describing the dynamics of a charged spin 1/2 particle with g-factor 2 moving in an arbitrary, spatially dependent, magnetic field in two spatial dimensions can be written as the anticommuator…

High Energy Physics - Phenomenology · Physics 2009-10-31 T. E. Clark , S. T. Love , S. R. Nowling