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In an attempt to improve on our earlier W3 theory [J. Chem. Phys. {\bf 120}, 4129 (2004)] we consider such refinements as more accurate estimates for the contribution of connected quadruple excitations ($\hat{T}_4$), inclusion of connected…

Chemical Physics · Physics 2007-05-23 Amir Karton , Elena Rabinovich , Jan M. L. Martin , Branko Ruscic

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

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

We extend the CCSDTQ implementation in CFOUR to UHF and ROHF references and demonstrate its efficiency. We apply it to basis set convergence of post-CCSDT(Q) corrections for the W4-08 thermochemical dataset. Convergence of…

Chemical Physics · Physics 2026-05-20 Aditya Barman , Gregory H. Jones , Jan M. L. Martin

In this tutorial-style review we discuss basic concepts of coupled cluster theory and recent developments that increase its computational efficiency for calculations of molecules, solids and materials in general. We will touch upon the…

Materials Science · Physics 2020-04-15 Igor Ying Zhang , Andreas Grüneis

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 discuss the theory and implementation of the finite temperature coupled cluster singles and doubles (FT-CCSD) method including the equations necessary for an efficient implementation of response properties. Numerical aspects of the…

Chemical Physics · Physics 2021-07-07 Alec F. White , Garnet Kin-Lic Chan

The method of sub-iteration, which was previously applied to the higher-order coupled cluster amplitude equations, is extended to the case of the coupled cluster $\Lambda$ equations. The sub-iteration procedure for the $\Lambda$ equations…

Chemical Physics · Physics 2025-03-26 Devin A. Matthews

A hierarchy of wavefunction composite methods (cWFT), based on G4- type cWFT methods available for elements H through Rn, was recently reported by Semidalas and Martin [J. Chem. Theor. Comput. 2020, 16, 4238]. We extend this hierarchy by…

Chemical Physics · Physics 2021-02-09 Emmanouil Semidalas , Jan M. L. Martin

With increasing engineering demands, there need high order accurate schemes embedded with precise physical information in order to capture delicate small scale structures and strong waves with correct "physics". There are two families of…

Numerical Analysis · Mathematics 2018-11-27 Jiequan Li

The coupled cluster method is considered a gold standard in quantum chemistry, reliably giving energies that are exact within chemical accuracy (1.6 mHartree). However, even in the CCSD approximation, where the cluster operator is truncated…

Chemical Physics · Physics 2023-03-10 Simon Elias Schrader , Simen Kvaal

Coupled cluster theory has had a momentous impact on the ab initio prediction of molecular properties, and remains a staple ingratiate in high-accuracy thermochemical model chemistries. However, these methods require inclusion of at least…

Chemical Physics · Physics 2025-03-26 James H. Thorpe , Zachary W. Windom , Rodney J. Bartlett , Devin A. Matthews

The optimized linear $\delta$-expansion is applied to the $\lambda \phi^4$ theory at high temperature. Using the imaginary time formalism the thermal mass is evaluated perturbatively up to order $\delta^2$. A variational procedure…

High Energy Physics - Phenomenology · Physics 2014-11-17 Marcus B. Pinto , Rudnei O. Ramos

We extend our assessment of the potential of perturbative coupled cluster (CC) expansions for a test set of open-shell atoms and organic radicals to the description of quadruple excitations. Namely, the second- through sixth-order models of…

Chemical Physics · Physics 2016-05-17 Janus J. Eriksen , Devin A. Matthews , Poul Jørgensen , Jürgen Gauss

Computationally efficient and accurate quantum mechanical approximations to solve the many-electron Schr\"odinger equation are at the heart of computational materials science. In that respect the coupled cluster hierarchy of methods plays a…

Materials Science · Physics 2022-01-11 Tina N. Mihm , Tobias Schäfer , Sai Kumar Ramadugu , Andreas Grüneis , James J. Shepherd

The thermochemistry of the carbon clusters C$_n$ (n=2--10) has been revisited by means of W4 theory and W3.2lite theory. Particularly the larger clusters exhibit very pronounced post-CCSD(T) correlation effects. Despite this, our best…

Chemical Physics · Physics 2010-08-26 Amir Karton , Alex Tarnopolsky , Jan M. L. Martin

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…

Introducing an active space approximation is inevitable for the quantum computations of chemical systems. However, this approximation ignores the electron correlations related to non-active orbitals. Here, we propose a computational method…

Quantum Physics · Physics 2024-06-06 Luca Erhart , Yuichiro Yoshida , Viktor Khinevich , Wataru Mizukami

Slater determinants have underpinned quantum chemistry for nearly a century, yet their full potential has remained challenging to exploit. In this work, we show that a variational wavefunction composed of a few hundred optimized…

Chemical Physics · Physics 2026-04-17 Clemens Giuliani , Jannes Nys , Rocco Martinazzo , Giuseppe Carleo , Riccardo Rossi

High granularity calorimeters have become increasingly crucial in modern particle physics experiments, and their importance is set to grow even further in the future. The CLUstering of Energy (CLUE) algorithm has shown excellent performance…

High Energy Physics - Experiment · Physics 2023-11-07 Erica Brondolin , Marco Rovere , Felice Pantaleo
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