r2SCAN-3c: A “Swiss army knife” composite electronic-structure method

The Journal of Chemical Physics, Journal Year: 2021, Volume and Issue: 154(6)

Published: Feb. 10, 2021

The recently proposed r2SCAN meta-generalized-gradient approximation (mGGA) of Furness and co-workers is used to construct an efficient composite electronic-structure method termed r2SCAN-3c. To this end, the unaltered functional combined with a tailor-made triple-ζ Gaussian atomic orbital basis set as well refitted D4 geometrical counter-poise corrections for London-dispersion superposition error. performance new evaluated GMTKN55 database covering large parts chemical space about 1500 data points, additional benchmarks non-covalent interactions, organometallic reactions, lattice energies organic molecules ices, adsorption on polar salt non-polar coinage-metal surfaces. These comprehensive tests reveal spectacular robustness r2SCAN-3c: It by far surpasses its predecessor B97-3c at only twice cost provides one best results all semi-local density-functional theory (DFT)/QZ methods ever tested one-tenth cost. Specifically, reaction conformational it outperforms prominent hybrid-DFT/QZ approaches two three orders magnitude lower Perhaps, most relevant remaining issue r2SCAN-3c self-interaction error (SIE), owing mGGA nature. However, SIE slightly reduced compared other (m)GGAs, demonstrated in examples. After all, remarkably robust chosen our group default, replacing previous DFT partially even expensive high-level standard applications systems up several hundreds atoms.

Language: Английский

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r2SCAN-D4: Dispersion corrected meta-generalized gradient approximation for general chemical applications

The Journal of Chemical Physics, Journal Year: 2021, Volume and Issue: 154(6)

Published: Feb. 9, 2021

We combine a regularized variant of the strongly constrained and appropriately normed semilocal density functional [J. Sun, A. Ruzsinszky, J. P. Perdew, Phys. Rev. Lett. 115, 036402 (2015)] with latest generation semi-classical London dispersion correction. The resulting approximation r2SCAN-D4 has speed generalized gradient approximations while approaching accuracy hybrid functionals for general chemical applications. demonstrate its numerical robustness in real-life settings benchmark molecular geometries, main group organo-metallic thermochemistry, as well non-covalent interactions supramolecular complexes crystals. Main transition metal bond lengths have errors just 0.8%, which is competitive molecules outperforms them complexes. weighted mean absolute deviation (WTMAD2) on large GMTKN55 database properties exceptionally small at 7.5 kcal/mol. This also holds organic reactions an MAD 3.3 versatile applicability to metal-organic systems transfers condensed systems, where lattice energies crystals are within (errors <1 kcal/mol).

Language: Английский

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Density functional theory methods applied to homogeneous and heterogeneous catalysis: a short review and a practical user guide

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(10), P. 7950 - 7970

Published: Jan. 1, 2024

The application of density functional theory (DFT) methods in catalysis has been growing fast the last few decades thanks to both availability more powerful high computing resources and development new efficient approximations approaches. DFT calculations allow for understanding crucial catalytic aspects that are difficult or even impossible access by experiments, thus contributing faster selective catalysts. Depending on system properties under investigation, different approaches should be used. Moreover, reliability obtained results deeply depends involved selected method model. This review addresses chemists, physicists materials scientists whose interest deals with DFT-based computational tools homogeneous heterogeneous catalysis. First, a brief introduction is presented. Then, main based atomic centered basis sets plane waves discussed, underlining differences, advantages limitations. Eventually, guidance towards selection model given, final focus evaluation energy barriers, which represents step all processes. Overall, rational practical guide beginners experienced users wide field

Language: Английский

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Photoswitchable imines: aryliminopyrazoles quantitatively convert to long-lived Z-isomers with visible light

Chemical Science, Journal Year: 2024, Volume and Issue: 15(11), P. 3872 - 3878

Published: Jan. 1, 2024

Simple structural modifications significantly boost the photochromic performance of imine-based photoswitches. This work lays a foundation for exploring new motifs in light-addressable dynamic combinatorial chemistry.

Language: Английский

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The Best of Both Worlds: ΔDFT Describes Multiresonance TADF Emitters with Wave-Function Accuracy at Density-Functional Cost

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 1114 - 1125

Published: Jan. 23, 2025

With their narrow-band emission, high quantum yield, and good chemical stability, multiresonance thermally activated delayed fluorescence (MR-TADF) emitters are promising materials for OLED technology. However, accurately modeling key properties, such as the singlet-triplet (ST) energy gap energy, remains challenging. While time-dependent density functional theory (TD-DFT), workhorse of computational science, suffers from fundamental issues, wave function-based coupled-cluster (CC) approaches, like approximate CC second-order (CC2), accurate but suffer cost unfavorable scaling with system size. This work demonstrates that a state-specific ΔDFT approach based on unrestricted Kohn-Sham (ΔUKS) combines best both worlds: diverse benchmark set 35 MR-TADF emitters, ΔUKS performs or better than CC2, recovering experimental ST gaps mean absolute deviation (MAD) 0.03 eV at small fraction CC2. When combined tuned range-separated LC-ωPBE functional, excellent performance extends to energies MR- donor-acceptor TADF even molecules an inverted (INVEST), rendering this jack all trades organic electronics.

Language: Английский

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Requirements for an accurate dispersion-corrected density functional

The Journal of Chemical Physics, Journal Year: 2021, Volume and Issue: 154(23)

Published: June 17, 2021

Post-self-consistent dispersion corrections are now the norm when applying density-functional theory to systems where non-covalent interactions play an important role. However, there is a wide range of base functionals and available from which choose. In this work, we opine on most desirable requirements ensure that both functional correction, individually, as accurate possible for non-bonded repulsion attraction. The should be dispersionless, numerically stable, involve minimal delocalization error. Simultaneously, correction include finite damping, higher-order pairwise terms, electronic many-body effects. These criteria essential avoiding reliance error cancellation obtaining correct results physics.

Language: Английский

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High solar-to-hydrogen efficiency photocatalytic hydrogen evolution reaction with the HfSe2/InSe heterostructure

Journal of Power Sources, Journal Year: 2022, Volume and Issue: 547, P. 232008 - 232008

Published: Sept. 1, 2022

Language: Английский

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Nanoscale MXene Interlayer and Substrate Adhesion for Lubrication: A Density Functional Theory Study

ACS Applied Nano Materials, Journal Year: 2022, Volume and Issue: 5(8), P. 10516 - 10527

Published: Aug. 8, 2022

Understanding the interlayer interaction at nanoscale in two-dimensional (2D) transition metal carbides and nitrides (MXenes) is important to improve their exfoliation/delamination process application (nano)-tribology. The layer-substrate also essential (nano)-tribology as effective solid lubricants should be resistant against peeling-off during rubbing. Previous computational studies considered MXenes' coupling with oversimplified, homogeneous terminations while neglecting underlying substrates. In our study, Ti-based MXenes both mixed are modeled using density functional theory (DFT). An ad hoc modified dispersion correction scheme used, capable of reproducing results obtained from a higher level theory. nature interactions, comprising van der Waals, dipole-dipole, hydrogen bonding, discussed along effects MXene sheet's thickness C/N ratio. Our demonstrate that play major role regulating substrate adhesion iron oxide and, therefore, lubrication, which affected by an external load. Using graphene MoS2 established references, we verify tribological performance can significantly improved avoiding -OH -F terminations, done controlling via post-synthesis processing.

Language: Английский

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Free and open source software for computational chemistry education

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2022, Volume and Issue: 12(5)

Published: March 23, 2022

Abstract After decades of waiting, computational chemistry for the masses is finally here. Our brief review on free and open source software (FOSS) packages points out existence offering a wide range functionality, all way from approximate semiempirical calculations with tight‐binding density functional theory to sophisticated ab initio wave function methods such as coupled‐cluster theory, covering both molecular solid‐state systems. Combined remarkable increase in computing power personal devices, which now rivals that fastest supercomputers world 1990s, we demonstrate decentralized model teaching possible thanks FOSS packages, enabling students perform reasonable modeling their own devices bring your device (BYOD) scheme. can be made trivially simple install keep up date, eliminating need departmental support, also enables comprehensive strategies, various algorithms' actual implementations used teaching. We exemplify what kinds are feasible four electronic structure programs, assuming only extremely modest resources, illustrate how enable approaches education within BYOD has further benefits driving its adoption: access code democratizes science chemistry, without limitation beyond education, academic industrial applications, example. This article categorized under: Software > Quantum Chemistry

Language: Английский

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Beyond Steric Crowding: Dispersion Energy Donor Effects in Large Hydrocarbon Ligands

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(9), P. 1337 - 1348

Published: April 15, 2022

ConspectusInteractions between sterically crowded hydrocarbon-substituted ligands are widely considered to be repulsive because of the intrusion electron clouds ligand atoms into each other's space, which results in Pauli repulsion. Nonetheless, there is another interaction less publicized but always present. This London dispersion (LD) can occur or molecules dipoles induced instantaneously, for example, H from C–H groups.These LD interactions attractive, their effects not as recognized those repulsion despite central role formation condensed matter. Their relatively poor recognition probably due relative weakness (ca. 1 kcal mol–1) individual H···H owing especially strong distance dependence. In contrast, where numerous interactions, a collective energy equaling several tens mol–1 may ensue. As result, some latent importance attraction energies emerges and assumes prominence that overshadow (e.g., stabilization high-oxidation-state transition-metal alkyls, inducing disproportionation reactions, otherwise unstable bonds).Despite being known over century, accurate quantification molecular species recent phenomenon at present based mainly on modified DFT calculations. A few leading reviews summarized these earlier studies C–H···H–C organic molecules, structures stabilities were described. inorganic organometallic have been recognized.The author's interest arose fortuitously decade ago during research heavier main-group element carbene analogues two-coordinate, open-shell (d1–d9) complexes counterintuitive steric observed. More detailed explanations provided by dispersion-corrected calculations collaboration with groups Tuononen Nagase (see below).This Account describes our development initial other classes. recently, work has led us move planned inclusion stabilize new types theoretical input Vasko Grimme below). Our approach sought use what described effect donor (DED) (i.e., spatially close-lying, densely packed substituents either −C6H2-2,4,6-Cy3, Cy = cyclohexyl) parts substituent) produce large compounds.We predict future design crowding hydrocarbon will include consideration incorporation standard methodology directed attainment synthetic targets.

Language: Английский

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