Extension of the D3 and D4 London Dispersion Corrections to the full Actinides Series

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(32), P. 21379 - 21394

Published: Jan. 1, 2024

Efficient dispersion corrections are an indispensable component of modern density functional theory, semi-empirical quantum mechanical, and even force field methods. In this work, we extend the well established D3 D4 London to full actinides series, francium, radium. To keep consistency with existing versions, original parameterization strategy model was only slightly modified. This includes improved reference Hirshfeld atomic partial charges at ωB97M-V/ma-def-TZVP level fit required electronegativity equilibration charge (EEQ) model. context, developed a new actinide data set called AcQM, which covers most common molecular compound space. Furthermore, efficient calculation dynamic polarizabilities that needed construct

Language: Английский

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Exploring the high sensitivity of DFT thermochemistry for protonation states of a ferredoxin model complex [CH3S4Fe2IIIS2H]−

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(16)

Published: April 22, 2025

Density functional theory (DFT) thermochemistry of 3d transition-metal complexes is well-known to be sensitive the amount exact Hartree–Fock exchange incorporated into exchange–correlation functional. For example, relative energies different protonation states iron–sulfur may vary by hundreds kJ/mol among DFT methods. In present study, we examine four isomers [CH3S4Fe2IIIS2H]− [2Fe–2S] ferredoxin model. Compared many-body ab initio phaseless auxiliary-field quantum Monte Carlo with multi-Slater determinant trial wavefunctions and fully connected singles doubles coupled-cluster perturbative triples methods, r2SCAN12-D4, B3LYP-D4, B97-1-D3(OP) approaches perform best. We also demonstrate that density-corrected on top KS-CCSD electronic densities provides reliable results r2SCAN Moreover, direct random phase approximation TPSSh, O3LYP, r2SCAN12 hybrid functionals performs well.

Language: Английский

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Analytical First Derivatives of the SCF Energy for the Conductor‐Like Polarizable Continuum Model With Non‐Static Radii

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(11)

Published: April 24, 2025

ABSTRACT Within this work, we present the derivation and implementation of analytical gradients for Gaussian‐switching (SwiG) Conductor‐like Polarizable Continuum Model (CPCM) with general nuclear coordinate‐dependent non‐static radii used creation van der Waals‐type cavities. This is done using recently presented dynamic adjustment continuum solvation ( Draco ) scheme. allows efficient geometry optimization reasonable numerical Hessian calculations. The derived gradient implemented in ORCA, therefore easily applicable. validated by comparing testing optimizations on a diverse test set, including small organic compounds, metal‐organic complexes, highly charged species. We additionally continuity potential energy surface an example where very strong changes occur. computational efficiency investigated.

Language: Английский

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An evaluation of local double hybrid density functionals

Chemical Physics Letters, Journal Year: 2025, Volume and Issue: unknown, P. 142048 - 142048

Published: March 1, 2025

Language: Английский

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Correction: The p-block challenge: assessing quantum chemistry methods for inorganic heterocycle dimerizations

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Correction for ‘The p-block challenge: assessing quantum chemistry methods inorganic heterocycle dimerizations’ by Thomas Gasevic et al. , Phys. Chem. 2024, 26 13884–13908, https://doi.org/10.1039/D3CP06217A.

Language: Английский

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Aquaporins-inspired MOF with CO2 recognition function in mixed matrix membrane for enhancing CO2/CH4 separation performance

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: 514, P. 163180 - 163180

Published: April 28, 2025

Language: Английский

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Software Update: The ORCA Program System—Version 6.0

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2025, Volume and Issue: 15(2)

Published: March 1, 2025

ABSTRACT Version 6.0 of the ORCA quantum chemistry program suite was released in July 2024. is a major turning point history since it represents near complete rewrite code base that leads to: (1) performance improvements, (2) clean and highly efficient greatly facilitates future development, (3) large amount new functionality, (4) interface capabilities facilitate inter‐operability with other packages. The article describes most salient features program.

Language: Английский

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Influence of Steric and Dispersion Interactions on the Thermochemistry of Crowded (Fluoro)alkyl Compounds

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 57(1), P. 153 - 163

Published: Dec. 15, 2023

ConspectusAlkanes play a pivotal role in industrial, environmental, and biological processes. They are characterized by their carbon–carbon single-bond structure, remarkable stability, conformational diversity. Fluorination of such compounds imparts unique physicochemical properties that often enhance pharmacokinetic profiles, metabolic receptor interactions while keeping beneficial properties. However, per- polyfluoroalkyl substances (PFAS) show persistent presence the environment potential adverse health effects, which propelled them to forefront global environmental discussions. Alkyl also prototypical for stereoelectronic (SE) effects widely applied chemistry. Substituents typically described as electron-density-donating/withdrawing and/or responsible sterically interacting with reagents or strategic groups molecule. That alkane branching can result higher stability compared less-branched isomers has been investigated detail testing quantum chemical methods, particular density functional theory (DFT). Alkane results spatially compact structures close intramolecular contacts so at specific size detailed balance attractive London dispersion covalent versus repulsive Pauli exchange shifts new, chemically unfragile situations. This may lead dissociation room temperature opens central question: what is smallest crowed cannot be made synthetically? In this Account, we try shed light on interplay among various (free) energy components crowded (fluoro)alkane dissociation. context, homolytic cleavage C–C bond series model alkanes increasing tert-butyl (tBu), adamantyl (Ad), [1.1.1]propellanyl (Prop) substituents investigated. Reference energies calculated PNO-LCCSD(T)-F12b level used benchmark performance contemporary DFT functionals. line previous conclusions, application corrections functionals mandatory. For structures, accurate description midrange correlation specifically van der Waals interactions, crucial, observed density-dependent VV10 correction superior D4 although asymptotic region better latter. The best available dispersion-inclusive systematic reasonably small residual errors safely large systems (>100 atoms), coupled cluster methods basis sets not computationally feasible anymore. qualitatively correct predictions synthetic accessibility under equilibrium conditions (free energy), inclusion thermostatistical (entropy) contributions essential. According our results, tetra-tert-butylmethane (C17tBu) largest most system positive free should synthesizable. difference between hydrogenated perfluorinated originates from increase steric repulsion substituents, compensated same extent orbital interactions. A sometimes-assumed similar demand fluorine hydrogen atoms corroborated investigations systems. Perfluorination found substantially decrease thermal rendering hexamethylethane (C8tBuF) last potentially stable representative.

Language: Английский

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Searching the Best Double-Hybrid Density Functional to Correctly Predict the Singlet–Triplet Excited-State Inversion in Organic Systems

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(43), P. 18313 - 18327

Published: Oct. 18, 2024

The theoretically disclosed, and experimentally confirmed, energy inversion of the lowest singlet (S1) triplet (T1) excited states organic molecules (i.e., Hund's rule violation) is investigated herein with aid modern nonempirically derived double-hybrid (DH) density functionals, in search best trade-off between accuracy computational cost viable electronic structure methods. For that purpose, we have selected a family parameter-free expressions differing their specific formulation (DFT-0DH, DFT-QIDH, DFT0-2, SOS1-DFT-0DH, SOS1-DFT-QIDH, SOS1-DFT0-2, RSX-DFT-0DH, RSX-DFT-QIDH, SOS1-RSX-DFT-0DH, SOS1-RSX-DFT-QIDH) as well underlying exchange–correlation functional used (PBE vs r2SCAN). sake evaluating which DH can correctly describe singlet–triplet excited-state inversion, second-order approximate singles doubles method spin-component scaling (SCS-CC2) equation-of-motion coupled cluster (EOM-CCSD) calculations are also carried out. results highlight importance delicate balance all terms composing correlation part being particularly significant for achieving most accurate results. We new (PBE-DH-INVEST) exploiting relationship, providing low error metrics expected to yield robust in, e.g., high-throughput studies.

Language: Английский

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A remarkably simple dispersion damping scheme and the DH24 double hybrid density functional

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(20)

Published: May 28, 2024

In recent papers, Becke et al. [J. Chem. Phys. 158, 151103 (2023)] and then 159, 241101 have developed a novel double hybrid density functional, “DH23,” whose terms are based on good local physics. Its 12 coefficients trained the GMTKN55 (general main-group thermochemistry, kinetics, noncovalent interactions) chemical database of Goerigk [Phys. 19, 32184 (2017)]. The lowest “WTMAD2” error to date for any or functional was obtained (1.73 kcal/mol revDH23 variant). Here, we simplify DH23 by introducing dispersion damping scheme involving atomic numbers only one global parameter. resulting new “DH24,” performs as well its predecessors.

Language: Английский

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