A Cost Effective Scheme for the Highly Accurate Description of Intermolecular Binding in Large Complexes DOI Open Access
Jiřı́ Czernek, Jiřı́ Brus, Vladimı́ra Czerneková

et al.

International Journal of Molecular Sciences, Journal Year: 2022, Volume and Issue: 23(24), P. 15773 - 15773

Published: Dec. 12, 2022

There has been a growing interest in quantitative predictions of the intermolecular binding energy large complexes. One most important quantum chemical techniques capable such is domain-based local pair natural orbital (DLPNO) scheme for coupled cluster theory with singles, doubles, and iterative triples [CCSD(T)], whose results are extrapolated to complete basis set (CBS) limit. Here, DLPNO-based focal-point method devised aim obtaining CBS-extrapolated values that very close their canonical CCSD(T)/CBS counterparts, thus may serve routinely checking performance less expensive computational methods, example, those based on density-functional (DFT). The efficacy this demonstrated several sets noncovalent complexes varying amounts electrostatics, induction, dispersion contributions (as revealed by accurate DFT-based symmetry-adapted perturbation (SAPT) calculations). It shown when applied dimeric models poly(3-hydroxybutyrate) chains its two polymorphic forms, DLPNO-CCSD(T) DFT-SAPT schemes agree within about 2 kJ/mol an absolute value interaction energy. These should be useful reliable description factors leading enthalpic stabilization extended systems.

Language: Английский

CREST—A program for the exploration of low-energy molecular chemical space DOI Creative Commons
Philipp Pracht, Stefan Grimme, Christoph Bannwarth

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(11)

Published: March 21, 2024

Conformer–rotamer sampling tool (CREST) is an open-source program for the efficient and automated exploration of molecular chemical space. Originally developed in Pracht et al. [Phys. Chem. Phys. 22, 7169 (2020)] as driver calculations at extended tight-binding level (xTB), it offers a variety molecular- metadynamics simulations, geometry optimization, structure analysis capabilities. Implemented algorithms include procedures conformational sampling, explicit solvation studies, calculation absolute entropy, identification protonation deprotonation sites. Calculations are set up to run concurrently, providing single-node parallelization. CREST designed require minimal user input comes with implementation GFNn-xTB Hamiltonians GFN-FF force-field. Furthermore, interfaces any quantum chemistry force-field software can easily be created. In this article, we present recent developments code show selection applications most important features program. An novelty refactored backend, which provides significant speed-up small or medium-sized drug molecules allows more sophisticated setups, example, mechanics/molecular mechanics minimum energy crossing point calculations.

Language: Английский

Citations

98
ωB97X-3c: A composite range-separated hybrid DFT method with a molecule-optimized polarized valence double-ζ basis set DOI
Marcel Müller, Andreas Hansen, Stefan Grimme

et al.

The Journal of Chemical Physics, Journal Year: 2022, Volume and Issue: 158(1)

Published: Dec. 12, 2022

A new composite density functional theory (DFT) method is presented. It based on ωB97X-V as one of the best-performing functionals for GMTKN55 thermochemistry database and completes family "3c" methods toward range-separated hybrid DFT. This consistently available all elements up to Rn (Z = 1-86). Its further key ingredients are a polarized valence double-ζ (vDZP) Gaussian basis set, which was fully optimized in molecular DFT calculations, combination with large-core effective core potentials specially adapted D4 dispersion correction. Unlike most existing atomic orbital sets, vDZP shows only small set superposition errors (BSSEs) can compete standard sets triple-ζ quality. Small residual BSSE effects efficiently absorbed by damping scheme, overall eliminates need an explicit treatment or empirical corrections BSSE. Thorough tests variety benchmark show that method, dubbed ωB97X-3c, par even outperforms quadruple-zeta at fraction computational cost. Particular strengths this description non-covalent interactions barrier heights, it among overall.

Language: Английский

Citations

65
State-of-the-art local correlation methods enable affordable gold standard quantum chemistry for up to hundreds of atoms DOI Creative Commons
Péter R. Nagy

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14556 - 14584

Published: Jan. 1, 2024

In this feature, we review the current capabilities of local electron correlation methods up to coupled cluster model with single, double, and perturbative triple excitations [CCSD(T)], which is a gold standard in quantum chemistry. The main computational aspects method types are assessed from perspective applications, but focus kept on how achieve chemical accuracy (

Language: Английский

Citations

11
Density functional theory for van der Waals complexes: Size matters DOI
Montgomery Gray, John M. Herbert

Annual reports in computational chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 61

Published: Jan. 1, 2024

Language: Английский

Citations

10
Comment on “Benchmarking Basis Sets for Density Functional Theory Thermochemistry Calculations: Why Unpolarized Basis Sets and the Polarized 6-311G Family Should Be Avoided” DOI Creative Commons
Montgomery Gray, Paige E. Bowling, John M. Herbert

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(36), P. 7739 - 7745

Published: Aug. 27, 2024

Language: Английский

Citations

10
Sorting drug conformers in enzyme active sites: the XTB way DOI
Bun Chan, William Harbutt Dawson, Takahito Nakajima

et al.

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(16), P. 12610 - 12618

Published: Jan. 1, 2024

An assessment of low-cost computational chemistry methods reveals the outstanding performance XTB1 for calculating relative binding energies chemically similar systems, notably conformers substrates in enzyme active sites.

Language: Английский

Citations

9
Good Practices in Database Generation for Benchmarking Density Functional Theory DOI Creative Commons
Amir Karton,

Marcelo Tavares de Oliveira

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2025, Volume and Issue: 15(1)

Published: Jan. 1, 2025

ABSTRACT The hundreds of density functional theory (DFT) methods developed over the past three decades are often referred to as “zoo” DFT approximations. In line with this terminology, numerous benchmark studies might be considered “safari” evaluation efforts, reflecting their abundance, diversity, and wide range application methodological aspects. These benchmarks have played a critical role in establishing dominant approach quantum chemical applications remain essential for selecting an appropriate method specific properties (e.g., reaction energy, barrier height, or noncovalent interaction energy) systems organic, inorganic, organometallic). vital tool both users selection developers design parameterization. This review provides best‐practice guidance on key aspects benchmarking, such quality reference values, dataset size, geometries, basis sets, statistical analysis, electronic availability data. Additionally, we present flowchart assist systematically choosing these aspects, thereby enhancing reliability reproducibility benchmarking studies.

Language: Английский

Citations

1
S66x8 noncovalent interactions revisited: new benchmark and performance of composite localized coupled-cluster methods DOI Creative Commons
Golokesh Santra, Emmanouil Semidalas, Nisha Mehta

et al.

Physical Chemistry Chemical Physics, Journal Year: 2022, Volume and Issue: 24(41), P. 25555 - 25570

Published: Jan. 1, 2022

The S66x8 noncovalent interactions benchmark has been re-evaluated at the "sterling silver" level, using explicitly correlated MP2-F12 near complete basis set limit, CCSD(F12*)/aug-cc-pVTZ-F12, and a (T) correction from conventional CCSD(T)/sano-V{D,T}Z+ calculations. revised reference value disagrees by 0.1 kcal/mol RMS with original Hobza its revision Brauer et al, but only 0.04 variety "bronze" level data in Kesharwani al., Aust. J. Chem. 71, 238-248 (2018). We then used these to assess performance of localized-orbital coupled cluster approaches without counterpoise corrections, such as PNO-LCCSD(T) implemented MOLPRO, DLPNO-CCSD (T1) ORCA, LNO-CCSD(T) MRCC, for their respective "Normal", "Tight", "very Tight" settings. also considered composite combining different sets cutoffs. Furthermore, order isolate convergence domain truncation error, aug-cc-pVTZ we compared PNO, DLPNO, LNO canonical CCSD(T). conclude that veryTight criteria performs very well "raw" (CP-uncorrected), struggles reproduce counterpoise-corrected numbers even veryVeryTight criteria: this means accurate results can be obtained either extrapolation large enough quench superposition error (BSSE) aug-cc-pV{Q,5}Z, or scheme Tight{T,Q}+1.11[vvTight(T) - Tight(T)]. In contrast, works best counterpoise, while is comparable DLPNO-CCSD(T1). Among more economical methods, highest accuracies are seen dRPA75-D3BJ, {\omega}B97M-V, {\omega}B97M(2), revDSD-PBEP86-D4, DFT(SAPT) TDEXX ATDEXX kernel.

Language: Английский

Citations

30
Accurate Calculation of Isomerization and Conformational Energies of Larger Molecules Using Explicitly Correlated Local Coupled Cluster Methods in Molpro and ORCA DOI
Hans‐Joachim Werner, Andreas Hansen

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(20), P. 7007 - 7030

Published: July 24, 2023

An overview of the approximations in explicitly correlated local coupled cluster methods PNO-LCCSD(T)-F12 Molpro and DLPNO-CCSD(T)F12 ORCA is given. Options to select domains projected atomic orbitals (PAOs), pair natural (PNOs), triples (TNOs) both programs are described compared detail. The two applied compute isomerization conformational energies ISOL24 ACONFL test sets, where former part GMTKN55 benchmark suite. Thorough studies basis set effects presented for selected systems. These revealed large intramolecular superposition that make it practically impossible reliably determine complete (CBS) limits without including terms. latter strongly reduce dependence at same time also errors caused by domain approximations. On these studies, method new reference above-mentioned sets. We confident our results should agree within a few tenths kcal mol-1 with (unknown) CCSD(T)/CBS values, which therefore allowed us define computational settings accurate moderate effort. With protocols, especially PNO-LCCSD(T)-F12b/AVTZ', reliable values comprehensive sets can be generated efficiently. This significantly advance development evaluation performance approximate electronic structure methods, improved density functional or machine learning approaches.

Language: Английский

Citations

20
High-Level Quantum Chemical Prediction of C–F Bond Dissociation Energies of Perfluoroalkyl Substances DOI
Wanutcha Lorpaiboon, Junming Ho

The Journal of Physical Chemistry A, Journal Year: 2023, Volume and Issue: 127(38), P. 7943 - 7953

Published: Sept. 18, 2023

In this study, 550 C-F bond dissociation energies (BDEs) of a variety per- and polyfluoroalkyl substances (PFASs) obtained from high-level DLPNO-CCSD(T)/CBS calculations were used to assess the accuracy contemporary density functional theory (DFT) semiempirical methods. gas phase BDEs fall between 404.9-550.7 kJ mol-1 M06-2X ωB97M-V in conjunction with aug-cc-pVTZ basis set predicted closest benchmark level mean absolute deviation (MAD) 7.3 8.3 mol-1, respectively. It was observed that DFT prediction errors increase degree fluorination system size. As such, previous model chemistry recommendations based on smaller nonfluorinated systems may not be carried over modeling energetics PFASs related systems.

Language: Английский

Citations

16