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We are proposing a new computational thermochemistry protocol denoted W3 theory, as a successor to W1 and W2 theory proposed earlier [Martin and De Oliveira, J. Chem. Phys. 111, 1843 (1999)]. The new method is both more accurate overall…

Chemical Physics · Physics 2007-05-23 A. Daniel Boese , Mikhal Oren , Onur Atasoylu , Jan M. L. Martin , Mihaly Kallay , Juergen Gauss

The exact factorization of the time-dependent electron-nuclear wavefunction has been employed successfully in the field of quantum molecular dynamics simulations for interpreting and simulating light-induced ultrafast processes. In this…

Chemical Physics · Physics 2021-09-29 Federica Agostini , E. K. U. Gross

Quantum Monte Carlo simulations of interacting electrons in solids often use Slater-Jastrow trial wave functions. The Jastrow function takes into account correlations between pairs of electrons. In simulations of solids, it is common to use…

Materials Science · Physics 2007-05-23 A. Garcia-Lekue , M. Nekovee , J. M. Pitarke , R. Gaudoin

The accurate but expensive product of geminals ansatz may be approximated by a geminal power, but this approach sacrifices size consistency. Here we show both analytically and numerically that a size consistent form very similar to the…

Strongly Correlated Electrons · Physics 2012-11-19 Eric Neuscamman

In truncated coupled-cluster (CC) theories, non-variational and/or generally complex ground-state energies can occur. This is due to the non-Hermitian nature of the similarity transformed Hamiltonian matrix in combination with CC…

Chemical Physics · Physics 2023-09-22 Tanner Culpitt , Erik I. Tellgren , Fabijan Pavosevic

We present three modifications to our recently introduced fast randomized iteration method for full configuration interaction (FCI-FRI) and investigate their effects on the method's performance for Ne, H$_2$O, and N$_2$. The initiator…

Computational Physics · Physics 2023-10-03 Samuel M. Greene , Robert J. Webber , Jonathan Weare , Timothy C. Berkelbach

Ab-initio quantum Monte Carlo (QMC) methods are a state-of-the-art computational approach to obtaining highly accurate many-body wave functions. Although QMC methods are widely used in physics and chemistry to compute ground-state energies,…

Chemical Physics · Physics 2022-01-21 Kousuke Nakano , Abhishek Raghav , Sandro Sorella

An extensive analysis has been carried out of the performance of standard families of basis sets with the hierarchy of coupled cluster methods CC2, CCSD, CC3 and CCSDT in computing selected Oxygen, Carbon and Nitrogen K-edge (vertical) core…

Chemical Physics · Physics 2019-08-13 Johanna P. Carbone , Lan Cheng , Rolf H. Myhre , Devin Matthews , Henrik Koch , Sonia Coriani

Most of the novel energy materials contain multiple elements occupying a single site in their lattice. The exceedingly large configurational space of these materials imposes challenges in determining their ground-state structures. Coulomb…

Materials Science · Physics 2025-07-04 Konstantin Köster , Tobias Binninger , Payam Kaghazchi

We study the accuracy of analytical wave function based many-body methods derived by energy minimization of a Jastrow-Feenberg ansatz for electrons (`Fermi hypernetted chain / Euler Lagrange' approach). Approximations to avoid the…

Other Condensed Matter · Physics 2019-06-05 Martin Panholzer , Raphael Hobbiger , Helga Böhm

Accurately modeling chemical reactions at the atomistic level requires high-level electronic structure theory due to the presence of unpaired electrons and the need to properly describe bond breaking and making energetics. Commonly used…

We outline ideas on desired properties for a new generation of effective core potentials (ECPs) that will allow valence-only calculations to reach the full potential offered by recent advances in many-body wave function methods. The key…

We present an efficient moment-based perturbation scheme for evaluating polarizability tensors of small molecules at a fraction of the computational cost of conventional energy-based approaches. Rather than applying explicit electric…

Chemical Physics · Physics 2026-05-26 Anoop Ajaya Kumar Nair , Julian Beßner , Timo Jacob , Elvar Örn Jónsson

The linear combination of atomic orbitals (LCAO) method uses a small basis set in exchange for expensive matrix element calculations. The most efficient approximation for the matrix element calculations is the two-center approximation (2CA)…

Materials Science · Physics 2025-10-16 Tyler C. Sterling

The $\Delta$-Self-Consistent-Field ($\Delta$SCF) method has been established as an accurate and computationally efficient approach for calculating absolute core electron binding energies for light elements up to chlorine, but relatively…

Materials Science · Physics 2022-10-12 Juhan Matthias Kahk , Johannes Lischner

Quantum chemistry simulations that accurately predict the properties of materials are among the most highly anticipated applications of quantum computing. It is widely believed that simulations running on quantum computers will allow for…

This study evaluates the precision of widely recognized quantum chemical methodologies, CCSD(T), DLPNO-CCSD(T) and localized ph-AFQMC, for determining the thermochemistry of main group elements. DLPNO-CCSD(T) and localized ph-AFQMC, which…

We present a stable and systematically improvable quantum Monte Carlo (QMC) approach to calculating excited-state energies, which we implement using our fast randomized iteration method for the full configuration interaction problem…

Computational Physics · Physics 2023-10-03 Samuel M. Greene , Robert J. Webber , James E. T. Smith , Jonathan Weare , Timothy C. Berkelbach

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…

Variational algorithms are a promising paradigm for utilizing near-term quantum devices for modeling electronic states of molecular systems. However, previous bounds on the measurement time required have suggested that the application of…