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The bond dissociation energies of a set of 44 3d transition metal-containing diatomics are computed with phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) utilizing a correlated sampling technique. We investigate molecules with H, N,…

We present a near-linear scaling formulation of the explicitly-correlated coupled-cluster singles and doubles with perturbative triples method (CCSD(T)$_{\overline{\text{F12}}}$) for high-spin states of open-shell species. The approach is…

Chemical Physics · Physics 2024-07-30 Ashutosh Kumar , Frank Neese , Edward F. Valeev

The extension of the highly-optimized local natural orbital (LNO) CCSD(T) method is presented for high-spin open-shell molecules. The techniques enabling the outstanding efficiency of the closed-shell LNO-CCSD(T) variant are adopted,…

Chemical Physics · Physics 2023-11-17 P. Bernát Szabó , József Csóka , Mihály Kállay , Péter R. Nagy

Quantum-mechanical methods are widely used for understanding molecular interactions throughout biology, chemistry, and materials science. Quantum diffusion Monte Carlo (DMC) and coupled cluster with single, double, and perturbative triple…

We report a scalable Fortran implementation of the phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) and demonstrate its excellent performance and beneficial scaling with respect to system size. Furthermore, we investigate…

Chemical Physics · Physics 2024-02-09 Z. Sukurma , M. Schlipf , M. Humer , A. Taheridehkordi , G. Kresse

Obtaining sub-chemical accuracy (1 kJ mol${}^{-1}$) for reaction energies of medium-sized gas-phase molecules is a longstanding challenge in the field of thermochemical modeling. The perturbative triples correction to CCSD, CCSD(T),…

Chemical Physics · Physics 2025-03-26 Tingting Zhao , James H. Thorpe , Devin A. Matthews

We introduce a black-box auxiliary field quantum Monte Carlo (AFQMC) approach to perform highly accurate electronic structure calculations using configuration interaction singles and doubles (CISD) trial states. This method consistently…

Two new schemes for computing molecular total atomization energies (TAEs) and/or heats of formation ($\Delta H^\circ_f$) of first-and second-row compounds to very high accuracy are presented. The more affordable scheme, W1 (Weizmann-1)…

Chemical Physics · Physics 2009-10-31 Jan M. L. Martin , Glenisson de Oliveira

The study and prediction of chemical reactivity is one of the most important application areas of molecular quantum chemistry. Large-scale, fully error-tolerant quantum computers could provide exact or near-exact solutions to the underlying…

Quantum Physics · Physics 2019-09-12 Michael Kühn , Sebastian Zanker , Peter Deglmann , Michael Marthaler , Horst Weiß

Accurate thermochemical data with sub-chemical accuracy (within 1 kcal mol$^{-1}$ of the empirical ground truth) are essential for advancing computational chemistry methods. However, existing datasets that reach this level of accuracy…

Transition metal complexes are ubiquitous in biology and chemical catalysis, yet they remain difficult to accurately describe with ab initio methods due to the presence of a large degree of dynamic electron correlation, and, in some cases,…

By judicious use of extrapolations to the 1-particle basis set limit and $n$-particle calibration techniques, total atomization energies of molecules with up to four heavy atoms can be obtained with calibration accuracy (1 kJ/mol or better,…

Chemical Physics · Physics 2007-05-23 Jan M. L. Martin

With the aim of establishing a framework to efficiently perform the practical application of quantum chemistry simulation on near-term quantum devices, we envision a hybrid quantum--classical framework for leveraging problem decomposition…

Reliable theoretical predictions of noncovalent interaction energies, which are important e.g. in drug-design and hydrogen-storage applications, belong to longstanding challenges of contemporary quantum chemistry. In this respect, the…

Chemical Physics · Physics 2016-06-06 Matúš Dubecký , René Derian , Petr Jurečka , Lubos Mitas , Pavel Hobza , Michal Otyepka

We report modifications of the ph-AFQMC algorithm that allow the use of large time steps and reliable time step extrapolation. Our modified algorithm eliminates size-consistency errors present in the standard algorithm when large time steps…

Chemical Physics · Physics 2024-03-06 Zoran Sukurma , Martin Schlipf , Moritz Humer , Amir Taheridehkordi , Georg Kresse

High-accuracy composite wavefunction methods like Weizmann-4 (W4) theory, high-accuracy extrapolated \textit{ab initio} thermochemistry (HEAT), and Feller-Peterson-Dixon (FPD) enable sub-kJ/mol accuracy in gas-phase thermochemical…

Chemical Physics · Physics 2024-04-12 Emmanouil Semidalas , Amir Karton , Jan M. L. Martin

This study benchmarks the GFN family of semiempirical methods (GFN1-xTB, GFN2-xTB, GFN0-xTB, and GFN-FF) against density functional theory (DFT) for the evaluation of optimized molecular geometries and electronic properties of small organic…

In this work, we present an overview of the phaseless auxiliary-field quantum Monte Carlo (ph- AFQMC) approach from a computational quantum chemistry perspective, and present a numerical assessment of its performance on main group chemistry…

Chemical Physics · Physics 2022-09-28 Joonho Lee , Hung Q. Pham , David R. Reichman

Quantum--Mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those…

Chemical Physics · Physics 2015-06-12 Michele Pavanello , Troy Van Voorhis , Lucas Visscher , Johannes Neugebauer

To make useful connections with experimental measurements, correlated electronic structure theories must accurately predict chemical properties in addition to energies. We present a finite-difference based algorithm to compute first-order…

Chemical Physics · Physics 2025-09-24 Leon Otis , Sri Gudivada , Marvin Friede , James Shee
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