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Benchmarks that span a broad swath of chemical space, such as GMTKN55, are very useful for assessing progress in the quest for more universal DFT functionals. We find that the WTMAD2 metrics for a great number of functionals show a clear…

Chemical Physics · Physics 2019-12-12 Golokesh Santra , Jan M. L. Martin

To better understand the thermochemical kinetics and mechanism of a specific chemical reaction, an accurate estimation of barrier heights (forward and reverse) and reaction energy are vital. Due to the large size of reactants and transition…

Chemical Physics · Physics 2022-08-24 Golokesh Santra , Rivka Calinsky , Jan M. L. Martin

For revDSD double hybrids, the G\"orling-Levy second-order perturbation theory component is an Achilles' Heel when applied to systems with significant near-degeneracy ("static") correlation. We have explored its replacement by the direct…

Chemical Physics · Physics 2021-06-10 Golokesh Santra , Emmanouil Semidalas , Jan M. L. Martin

A long range corrected range separated hybrid functional is developed based on the density matrix expansion (DME) based semilocal exchange hole with Lee-Yang-Parr (LYP) correlation. An extensive study involving the proposed range separated…

Materials Science · Physics 2017-09-05 Subrata Jana , Bikash Patra , Hemanadhan Myneni , Prasanjit Samal

We have compared the performance of Grimme style DH/DSD and Zhang-Xu-Goddard type xDH/xDSD forms for double hybrids. In the DH and DSD forms, KS orbitals with elevated HF exchange and damped DFT correlation are used, while in the xDH and…

Chemical Physics · Physics 2015-11-12 Manoj Kumar Kesharwani , Sebastian Kozuch , Jan M. L. Martin

The accuracy of applying density functional theory to noncovalent interactions is hindered by errors arising from low-density regions of interaction-induced change in the density gradient, error compensation between correlation and exchange…

Chemical Physics · Physics 2014-10-22 Marcin Modrzejewski , Grzegorz Chałasiński , Małgorzata M. Szczęśniak

Double hybrid density functional theory arguably sits on the seamline between wavefunction methods and DFT: it represents a special case of Rung 5 on the "Jacobs Ladder" of John P. Perdew. For large and chemically diverse benchmarks such as…

Chemical Physics · Physics 2020-10-16 Jan M. L. Martin , Golokesh Santra

We devise a scheme for converting an existing exchange functional into its range-separated hybrid variant. The underlying exchange hole of the Becke-Roussel type has the exact second-order expansion in the interelectron distance. The…

Chemical Physics · Physics 2016-09-19 Marcin Modrzejewski , Michal Hapka , Grzegorz Chalasinski , Malgorzata M. Szczesniak

A range-separated double-hybrid (RSDH) scheme which generalizes the usual range-separated hybrids and double hybrids is developed. This scheme consistently uses a two-parameter Coulomb-attenuating-method (CAM)-like decomposition of the…

Chemical Physics · Physics 2018-05-23 Cairedine Kalai , Julien Toulouse

The large and chemically diverse GMTKN55 benchmark was used as a training set for parametrizing composite wave function thermochemistry protocols akin to G4(MP2)XK theory (Chan et al, JCTC 2019, 15, 4478-4484). Even after reparametrization,…

Chemical Physics · Physics 2020-10-16 Emmanouil Semidalas , Jan M. L. Martin

For the large and chemically diverse GMTKN55 benchmark suite, we have studied the performance of density-corrected density functional theory (HF-DFT), compared to self-consistent DFT, for several pure and hybrid GGA and meta-GGA…

Chemical Physics · Physics 2021-03-29 Golokesh Santra , Jan M. L. Martin

Range separated hybrid density functionals are very successful in describing a wide range of molecular and solid state properties accurately. Range separated hybrid functionals are designed from spherically averaged or system averaged…

Materials Science · Physics 2017-12-15 Subrata Jana , Prasanjit Samal

We have investigated the effect of F12 geminals on the basis set convergence of harmonic frequencies calculated using two representative double-hybrid density functionals, namely B2GP-PLYP and revDSD-PBEP86-D4. Like previously found for…

Chemical Physics · Physics 2022-12-27 Nisha Mehta , Golokesh Santra , Jan M. L. Martin

Density-functional theory (DFT) has become the workhorse of modern computational chemistry, with dispersion corrections such as the exchange-hole dipole moment (XDM) model playing a key role in high-accuracy modelling of large-scale…

Chemical Physics · Physics 2026-05-22 Kyle R. Bryenton , Erin R. Johnson

Dielectric-dependent hybrid (DDH) functionals were recently shown to yield accurate energy gaps and dielectric constants for a wide variety of solids, at a computational cost considerably less than that of GW calculations. The fraction of…

Materials Science · Physics 2016-06-08 Jonathan H Skone , Marco Govoni , Giulia Galli

Quantum chemistry methods exploiting density-functional approximations for short-range electron-electron interactions and second-order M{{\o}}ller-Plesset (MP2) perturbation theory for long-range electron-electron interactions have been…

Density-functional theory (DFT) has become the workhorse of modern computational chemistry, with dispersion corrections such as the exchange-hole dipole moment (XDM) model playing a key role in high-accuracy modelling of large-scale…

Chemical Physics · Physics 2025-06-04 Kyle R Bryenton , Erin R Johnson

Recently developed fused-ring electron-acceptors such as Y6 (BTP-4F) have strong oscillator strength, good charge-carrier transport and a small bandgap. They therefore have enormous current technical application to organic optoelectronics,…

Materials Science · Physics 2026-05-15 Tom Ward , Isabel Creed , Tim Rein , Jarvist Moore Frost

The most accurate theoretical method to describe excitons is the solution of the Bethe-Salpeter equation in the GW approximation (GW-BSE). However, because of its computation cost, time-dependent density functional theory (TDDFT) is…

Materials Science · Physics 2023-01-11 Rita Maji , Elena Degoli , Monica Calatayud , Valérie Véniard , Eleonora Luppi

We construct range-separated double-hybrid schemes which combine coupled-cluster or random-phase approximations with a density functional based on a two-parameter Coulomb-attenuating-method-like decomposition of the electron-electron…

Chemical Physics · Physics 2020-01-29 Cairedine Kalai , Bastien Mussard , Julien Toulouse
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