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Short-range corrections to long-range selected configuration interaction calculations are derived from perturbation theory considerations and applied to harmonium (with two to six electrons for some low-lying states). No fitting to reference data is used, and the method is applicable to ground and excited states. The formulas derived are rigorous when the physical interaction is approached. In this regime, the second-order expression provides a lower bound to the long-range full configuration interaction energy. A long-range/short-range separation of the interaction between electrons at a distance of the order of one atomic unit provides total energies within chemical accuracy, and, for the systems studied, provide better results than short-range density functional approximations.

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Electronic resonances are metastable states that can decay by electron loss. They are ubiquitous across various fields of science, such as chemistry, physics, and biology. However, current theoretical and computational models for resonances cannot yet rival the level of accuracy achieved by bound-state methodologies. Here, we generalize selected configuration interaction (SCI) to treat resonances using the complex absorbing potential (CAP) technique. By modifying the selection procedure and the extrapolation protocol of standard SCI, the resulting CAP-SCI method yields resonance positions and widths of full configuration interaction quality. Initial results for the shape resonances of \ce{N2-} and \ce{CO-} reveal the important effect of high-order correlation, which shifts the values obtained with CAP-augmented equation-of-motion coupled-cluster with singles and doubles by more than \SI{0.1}{\eV}. The present CAP-SCI approach represents a cornerstone in the development of highly-accurate methodologies for resonances.

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ipie is a Python-based auxiliary-field quantum Monte Carlo (AFQMC) package that has undergone substantial improvements since its initial release [J. Chem. Theory Comput., 2022, 19(1): 109-121]. This paper outlines the improved modularity and new capabilities implemented in ipie. We highlight the ease of incorporating different trial and walker types and the seamless integration of ipie with external libraries. We enable distributed Hamiltonian simulations, allowing for multi-GPU simulations of large systems. This development enabled us to compute the interaction energy of a benzene dimer with 84 electrons and 1512 orbitals, which otherwise would not have fit on a single GPU. We also support GPU-accelerated multi-slater determinant trial wavefunctions [arXiv:2406.08314] to enable efficient and highly accurate simulations of large-scale systems. This allows for near-exact ground state energies of multi-reference clusters, [Cu$_2$O$_2$]$^{2+}$ and [Fe$_2$S$_2$(SCH$_3$)]$^{2-}$. We also describe implementations of free projection AFQMC, finite temperature AFQMC, AFQMC for electron-phonon systems, and automatic differentiation in AFQMC for calculating physical properties. These advancements position ipie as a leading platform for AFQMC research in quantum chemistry, facilitating more complex and ambitious computational method development and their applications.

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Hedin's equations provide an elegant route to compute the exact one-body Green's function (or propagator) via the self-consistent iteration of a set of non-linear equations. Its first-order approximation, known as $GW$, corresponds to a resummation of ring diagrams and has shown to be extremely successful in physics and chemistry. Systematic improvement is possible, although challenging, via the introduction of vertex corrections. Considering anomalous propagators and an external pairing potential, we derive a new self-consistent set of closed equations equivalent to the famous Hedin equations but having as a first-order approximation the particle-particle (pp) $T$-matrix approximation where one performs a resummation of the ladder diagrams. This pp version of Hedin's equations offers a way to go systematically beyond the $T$-matrix approximation by accounting for low-order pp vertex corrections.

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Sujets

Atom A posteriori Localization Biodegradation Pesticide Atomic processes Quantum chemistry Ab initio calculation AROMATIC-MOLECULES BENZENE MOLECULE Atomic charges Petascale Anderson mechanism Coupled cluster Excited states A priori Localization Time reversal violation Single-core optimization Quantum Monte Carlo 3115vj Configuration interactions Electron electric dipole moment Polarizabilities AB-INITIO CALCULATION Electron electric moment Atoms CIPSI Atomic and molecular structure and dynamics Density functional theory Hyperfine structure Ground states 3115vn BSM physics Théorie des perturbations Dipole Fonction de Green Abiotic degradation 3115bw 3115ae Aimantation Atomic and molecular collisions Dirac equation Approximation GW Corrélation électronique Quantum Chemistry Diffusion Monte Carlo Pesticides Metabolites Clustering Molecular modeling Environmental fate Partial least squares Azide Anion Acrolein Relativistic corrections Molecular properties CP violation Electron correlation Time-dependent density-functional theory Large systems Wave functions X-ray spectroscopy États excités Ion 3315Fm New physics AB-INITIO 3115aj Argile Numerical calculations Valence bond Rydberg states Spin-orbit interactions 3115ag Green's function Molecular descriptors Range separation Carbon Nanotubes QSAR 3115am Atomic charges chemical concepts maximum probability domain population Analytic gradient Diatomic molecules Xenon 3470+e Line formation ALGORITHM Parallel speedup Coupled cluster calculations Argon Auto-énergie Parity violation Mécanique quantique relativiste Chemical concepts Chimie quantique Atrazine-cations complexes Relativistic quantum chemistry Perturbation theory Configuration Interaction Dispersion coefficients Atomic data BIOMOLECULAR HOMOCHIRALITY Atrazine Adiabatic connection Configuration interaction Relativistic quantum mechanics

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