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Related papers: W4 theory for computational thermochemistry: in pu…

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The (T) and [T] perturbative corrections are derived for multicomponent coupled-cluster theory with single and double excitations (CCSD). Benchmarking shows that multicomponent CCSD methods that include the perturbative corrections are more…

Chemical Physics · Physics 2022-07-01 Dylan Fowler , Kurt R. Brorsen

Minimally empirical G4-like composite wavefunction theories [E. Semidalas and J. M. L. Martin, \textit{J. Chem. Theory Comput.} {\bf 16}, 4238-4255 and 7507-7524 (2020)] trained against the large and chemically diverse GMTKN55 benchmark…

Chemical Physics · Physics 2024-04-05 Emmanouil Semdalas , Jan M. L. Martin

The high-accuracy W4 computational thermochemistry protocol, and several post-W4 methods, have been applied to the P$_2$ and P$_4$ molecules. Contrary to previous studies, we find the experimental thermochemistry to be fundamentally sound.…

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

The present work proposes an approach to obtain a basis-set correction based on density-functional theory (DFT) for the computation of molecular properties in wave-function theory (WFT). This approach allows one to accelerate the basis-set…

Chemical Physics · Physics 2022-05-18 Diata Traore , Julien Toulouse , Emmanuel Giner

We present the first application to real molecular systems of the recently proposed linear-response theory for the density-based basis-set correction method [J. Chem. Phys. 158, 234107 (2023)]. We apply this approach to accelerate the…

Chemical Physics · Physics 2024-02-27 Diata Traore , Julien Toulouse , Emmanuel Giner

Within the framework of many-body perturbation theory based on Green's functions, the $GW$ approximation has emerged as a pivotal method for computing quasiparticle energies and excitation spectra. However, its high computational cost and…

Chemical Physics · Physics 2025-12-25 Yueyang Zhang , Wei Wu , Peifeng Su

A new state specific correlation correction to configuration interaction singles (CIS) excitation energies is preseted using coupled cluster perturbation theory (CCPT). General expressions for CIS-CCPT are derived and expanded explicitly to…

Chemical Physics · Physics 2015-06-19 Jason N. Byrd , Victor F. Lotrich , Rodney J. Bartlett

The heats of formation of HClO$_4$ and Cl$_2$O$_7$ have been determined to chemical accuracy for the first time by means of W1 and W2 theory. These molecules exhibit particularly severe degrees of inner polarization, and as such obtaining a…

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

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 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

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

Computation of heats of reaction of large molecules is now feasible using domain-based PNO-CCSD(T) theory. However, to obtain agreement within 1~kcal/mol of experiment, it is necessary to eliminate basis set incompleteness error, which…

Chemical Physics · Physics 2023-09-07 Kesha Sorathia , Damyan Frantzov , David P. Tew

Here we demonstrate workably accurate estimation of optical excitation threshold for large systems comprising of hundreds of atoms through an anti-causally corrected(ACC) real-time dynamics(RTD) approach implemented in a minimal…

Materials Science · Physics 2023-06-13 Joydev De , Manoar Hossain , Joydeep Bhattacharjee

Charged excitations of the oligoacene family of molecules, relevant for astrophysics and technological applications, are widely studied and therefore provide an excellent system for benchmarking theoretical methods. In this work, we…

Chemical Physics · Physics 2016-05-18 Tonatiuh Rangel , Samia M. Hamed , Fabien Bruneval , Jeffrey B. Neaton

A major difficulty in quantum simulation is the adequate treatment of a large collection of entangled particles, synonymous with electron correlation in electronic structure theory, with coupled cluster (CC) theory being the leading…

Chemical Physics · Physics 2024-06-06 Zachary W. Windom , Daniel Claudino , Rodney J. Bartlett

We describe our efforts of the past few years to create a large set of more than 500 highly-accurate vertical excitation energies of various natures ($\pi \to \pi^*$, $n \to \pi^*$, double excitation, Rydberg, singlet, doublet, triplet,…

The quasi-chemical organization of the potential distribution theorem -- molecular quasi-chemical theory (QCT) -- enables practical calculations and also provides a conceptual framework for molecular hydration phenomena. QCT can be viewed…

Chemical Physics · Physics 2021-05-14 Dilipkumar N. Asthagiri , Michael E. Paulaitis , Lawrence R. Pratt

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…

Quantum chemistry simulations offer a cost-effective way for computational design of BODIPY photosensitizers with potential use in photodynamic therapy (PDT). However, accurate predictions of photophysical properties, such as excitation…

The $GW$ approximation has been recently gaining popularity among the method for simulating molecular core-level X-ray photoemission spectra. Traditionally, $GW$ core-level binding energies have been computed using either the cc-pV$n$Z or…

Chemical Physics · Physics 2022-07-13 Daniel Mejia-Rodriguez , Alexander Kunitsa , Edoardo Aprà , Niranjan Govind