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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Zero-field splitting parameters within exact two-component theory and modern density functional theory using seminumerical integration

The Journal of Chemical Physics, Journal Year: 2023, Volume and Issue: 159(19)

Published: Nov. 21, 2023

An efficient implementation of zero-field splitting parameters based on the work Schmitt et al. [J. Chem. Phys. 134, 194113 (2011)] is presented. Seminumerical integration techniques are used for two-electron spin-dipole contribution and response equations spin-orbit perturbation. The original formulation further generalized. First, it extended to meta-generalized gradient approximations local hybrid functionals. For these functional classes, paramagnetic current density considered in coupled-perturbed Kohn-Sham perturbation term. Second, formulated within relativistic exact two-component theory screened nuclear (SNSO) approximation. accuracy demonstrated transition-metal diatomic main-group compounds. efficiency assessed Mn Mo complexes. Here, found that coarse grids seminumerical schemes lead drastic speedups while introducing clearly negligible errors. In addition, SNSO approximation substantially reduces computational demands leads very similar results as mean field Ansatz.

Language: Английский

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

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(18), P. 13884 - 13908

Published: Jan. 1, 2024

We present a benchmark set of dimerization energies “inorganic benzenes” composed all non-carbon p-block elements main groups III to VI up polonium representing challenge contemporary quantum chemical methods.

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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Modeling the Monolayer Formation of Merocyanine HB238 on the Ag(100) Surface

The Journal of Physical Chemistry C, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

Language: Английский

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