Spin–State Energetics for Hydride and Helium Models of Transition Metal Complexes: A Benchmark Study of Wave Function Quantum Chemistry Methods DOI Creative Commons
Mariusz Radoń

Опубликована: Авг. 16, 2024

Accurate determination of spin–state energetics in first-row transition metal (TM) complexes is recognized as a challenging problem computational quantum chemistry because different methods often yield divergent predictions and credible reference data are scarce. Trying to provide way towards unambiguously accurate values from high-level wave function computation, benchmark set small TM with hydrides (H^–) or helium atoms σ-donor ligands presented. These models have analogous electronic structures realistic their feature comparable method- dependence, but size enables application more than applicable complexes. The extrapolated full configuration interaction (exFCI) results obtained for selected splittings the hydride/helium used benchmarking various methods, including second- third-order perturbation theory multireference CI, coupled cluster up approximate quadruples. It demonstrated that exFCI can be reproduced satisfactorily both single-reference among which NEVPT2 CCSDT(Q)_Λ perform best, yielding deviations uncertainties smaller 2 kcal/mol. CCSD(T) method yields errors ca. 3 kcal/mol smaller, one exception where CCSD(T)’s error greater 6 presumably due pronounced character. CASPT2, CASPT3, CASPT2/CC shown not outperform consistently. present study, addition presenting novel problem, establishes useful systems further investigations correlated structure methods.

Язык: Английский

Beyond CCSD(T) Accuracy at Lower Scaling with Auxiliary Field Quantum Monte Carlo DOI
Ankit Mahajan, James H. Thorpe, Jo S. Kurian

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

We introduce a black-box auxiliary field quantum Monte Carlo (AFQMC) approach to perform highly accurate electronic structure calculations using configuration interaction singles and doubles (CISD) trial states. This method consistently provides more energy estimates than coupled cluster with perturbative triples (CCSD(T)), often regarded as the gold standard in chemistry. level of precision is achieved at lower asymptotic computational cost, scaling O(N6) compared O(N7) CCSD(T). provide numerical evidence supporting these findings through results for challenging main group transition metal-containing molecules.

Язык: Английский

Процитировано

1
Benchmarking Molecular and Periodic Extended Tight Binding Methods for Spin-State Energies in Spin-Crossover Systems DOI
Silvia Gómez‐Coca, Eliseo Ruíz

The Journal of Physical Chemistry C, Год журнала: 2025, Номер unknown

Опубликована: Фев. 13, 2025

Язык: Английский

Процитировано

1
Predicting Spin States of Iron Porphyrins with DFT Methods Including Crystal Packing Effects and Thermodynamic Corrections DOI
Mariusz Radoń

Physical Chemistry Chemical Physics, Год журнала: 2024, Номер 26(26), С. 18182 - 18195

Опубликована: Янв. 1, 2024

Which DFT methods can most reliably predict the observed spin state in iron porphyrins with thermodynamics and crystal packing included?

Язык: Английский

Процитировано

3
Projector‐Based Quantum Embedding Study of Iron Complexes DOI Open Access
Jonathan M. Waldrop, Ajay Panyala, Daniel Mejı́a-Rodrı́guez

и другие.

Journal of Computational Chemistry, Год журнала: 2025, Номер 46(3)

Опубликована: Янв. 29, 2025

ABSTRACT Projection‐based embedding theory (PBET) is used to calculate and assess the challenging spin‐crossover energies for a selection of small Fe‐containing systems by metal center into frozen potential ligands. MP2, CCSD, CCSD(T) are embedded in potentials from SCAN r 2 functionals compared with canonical values constituent methods previously reported reference values. Considering PBET calculations as correction underlying DFT, able provided improvement most cases. In some cases, compensate limitations wave function produce results similar more rigorous literature. For near zero, current methodology fails provide consistent improvement. The isolated recalculation electronic structure around when DFT treatment ligand field shows promise pragmatic lower cost whole system difficult class complexes.

Язык: Английский

Процитировано

0
Performance of Quantum Chemistry Methods for Benchmark Set of Spin–State Energetics Derived from Experimental Data of 17 Transition Metal Complexes (SSE17) DOI Creative Commons
Mariusz Radoń, Gabriela Drabik, Maciej Hodorowicz

и другие.

Chemical Science, Год журнала: 2024, Номер 15(48), С. 20189 - 20204

Опубликована: Янв. 1, 2024

Accurate prediction of spin-state energetics for transition metal (TM) complexes is a compelling problem in applied quantum chemistry, with enormous implications modeling catalytic reaction mechanisms and computational discovery materials. Computed are strongly method-dependent credible reference data scarce, making it difficult to conduct conclusive studies open-shell TM systems. Here, we present novel benchmark set first-row energetics, which derived from experimental 17 containing FeII, FeIII, CoII, CoIII, MnII, NiII chemically diverse ligands. The estimates adiabatic or vertical splittings, obtained spin crossover enthalpies energies spin-forbidden absorption bands, suitably back-corrected the vibrational environmental effects, employed as values benchmarking density functional theory (DFT) wave function methods. results demonstrate high accuracy coupled-cluster CCSD(T) method, features mean absolute error (MAE) 1.5 kcal mol-1 maximum -3.5 mol-1, outperforms all tested multireference methods: CASPT2, MRCI+Q, CASPT2/CC CASPT2+δMRCI. Switching Hartree-Fock Kohn-Sham orbitals not found consistently improve accuracy. best performing DFT methods double-hybrids (PWPB95-D3(BJ), B2PLYP-D3(BJ)) MAEs below 3 errors within 6 whereas so far recommended states (e.g., B3LYP*-D3(BJ) TPSSh-D3(BJ)) perform much worse 5-7 beyond 10 mol-1. This work first such extensive study chemistry use data. relevant proper choice characterize systems catalysis (bio)inorganic may also stimulate new developments quantum-chemical machine learning approaches.

Язык: Английский

Процитировано

1
Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes DOI
Aleksandr A. Chamkin,

Elena S. Chamkina

Journal of Computational Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Июль 25, 2024

The present computational study provides a benchmark of density functional theory (DFT) methods in describing hydrogen evolution processes catalyzed by [Cp*Rh]-containing organometallic complexes. A test set was composed 26 elementary reactions featuring chemical transformations and bonding situations essential for the field, including emerging concept non-innocent Cp* behavior. Reference values were obtained from highly accurate 3/4 complete basis 6/7 PNO space extrapolated DLPNO-CCSD(T) energies. performance lower-level extrapolation procedures also assessed. We considered 84 functionals (DF) (including 13 generalized gradient approximations (GGA), nine meta-GGAs, 33 hybrids, 29 double-hybrids) three composite (HF-3c, PBEh-3c, r

Язык: Английский

Процитировано

1
Predicting Spin States of Iron Porphyrins with DFT Methods Including Crystal Packing Effects and Thermodynamic Corrections DOI Creative Commons
Mariusz Radoń

Опубликована: Март 29, 2024

Accurate computational treatment of spin states for transition metal complexes, exemplified by iron porphyrins, lies at the heart quantum bioinorganic chemistry, but same time represents a great challenge approximate density functional theory (DFT) methods, which are predominantly used. Here, accuracy DFT methods spin–state splittings in porphyrin is assessed probing ability to correctly predict ground six Fe(III) or Fe(II) complexes experimentally characterized solid state. For each case, molecular and periodic calculations employed quantify effect side substituents crystal packing (CPE) on splitting. It proposed partition total CPE into additive components, direct structural one, importance shown significantly vary from case case. By knowing substituent effect, CPE, Gibbs free energy thermodynamic correction calculations, one can employ experimental ground-state information order derive quantitative constraint electronic difference simplified (porphin) model metalloporphyrin. The constraints derived such way—in form single double inequalities—are used assess dispersion-corrected 6 [Fe(III)(P)(2-MeIm)2]+, [Fe(III)(P)(2-MeIm)]+, [Fe(II)(P)(THF)2] [Fe(II)(P)] models (where P porphin, 2-MeIm 2-methylimidazole, THF tetrahydrofuran). These data constitute new benchmark set crystalline porphyrins (SSCIP6). highest obtained double-hybrid functionals (B2PLYP-D3, DSD-PBEB95-D3), whereas hybrid functionals, especially those with reduced admixture exact exchange (B3LYP*-D3, TPSSh-D3), found considerably overstabilize intermediate state, leading incorrect prediction porphyrins. present approach, be generalized other not only useful method benchmarking, also sheds light interpretations metalloporphyrins, important understand properties heme proteins.

Язык: Английский

Процитировано

0
Notizen aus der Chemie DOI

Lena Barra,

Johanna Heine, Constantin Hoch

и другие.

Nachrichten aus der Chemie, Год журнала: 2024, Номер 72(6), С. 52 - 55

Опубликована: Май 31, 2024

Процитировано

0
Performance of Quantum Chemistry Methods for Benchmark Set of Spin–State Energetics Derived from Experimental Data of 17 Transition Metal Complexes (SSE17) DOI Creative Commons
Mariusz Radoń, Gabriela Drabik, Maciej Hodorowicz

и другие.

Опубликована: Авг. 1, 2024

Reliable prediction of spin-state energetics for transition metal (TM) complexes is recognized as a challenging and compelling problem in quantum chemistry, with implications modeling catalytic reaction mechanisms computational discovery materials. The computed spin–state are highly variable the choice method credible reference data scarce, making it difficult to conduct conclusive studies open-shell TM systems. Here, we present novel benchmark set first-row energetics, which derived from curated experimental 17 representative containing Fe(II), Fe(III), Co(II), Co(III), Mn(II), Ni(II) chemically diverse ligands. values adiabatic or vertical energy differences spin-crossover enthalpies (9 complexes) energies spin-forbidden absorption bands reflectance spectra (8 complexes). These carefully back-corrected relevant vibrational environmental effects (due solvation crystal lattice) order provide directly comparable electronic differences. new makes possible assess accuracy approximate density functional theory (DFT) wave function methods level statistical reliability not attained earlier studies. lowest mean absolute error (MAE) 1.5 kcal/mol maximum −3.5 found coupled-cluster CCSD(T) method, outperforms all tested multireference methods: CASPT2, MRCI+Q, CASPT2/CC CASPT2+δMRCI. Contrary claims literature, use Kohn–Sham instead Hartree–Fock orbitals determinant consistently improve energetics. best performing DFT double-hybrids (PWPB95-D3(BJ), B2PLYP-D3(BJ)) MAEs below 3 errors within 6 kcal/mol, whereas traditionally recommended spin states (e.g., B3LYP*-D3(BJ) TPSSh-D3(BJ)) perform much worse 5–7 beyond 10 kcal/mol. results this work proper characterize systems catalysis (bio)inorganic may also stimulate developments quantum-chemical machine learning approaches.

Язык: Английский

Процитировано

0
Spin–State Energetics for Hydride and Helium Models of Transition Metal Complexes: A Benchmark Study of Wave Function Quantum Chemistry Methods DOI Creative Commons
Mariusz Radoń

Опубликована: Авг. 16, 2024

Accurate determination of spin–state energetics in first-row transition metal (TM) complexes is recognized as a challenging problem computational quantum chemistry because different methods often yield divergent predictions and credible reference data are scarce. Trying to provide way towards unambiguously accurate values from high-level wave function computation, benchmark set small TM with hydrides (H^–) or helium atoms σ-donor ligands presented. These models have analogous electronic structures realistic their feature comparable method- dependence, but size enables application more than applicable complexes. The extrapolated full configuration interaction (exFCI) results obtained for selected splittings the hydride/helium used benchmarking various methods, including second- third-order perturbation theory multireference CI, coupled cluster up approximate quadruples. It demonstrated that exFCI can be reproduced satisfactorily both single-reference among which NEVPT2 CCSDT(Q)_Λ perform best, yielding deviations uncertainties smaller 2 kcal/mol. CCSD(T) method yields errors ca. 3 kcal/mol smaller, one exception where CCSD(T)’s error greater 6 presumably due pronounced character. CASPT2, CASPT3, CASPT2/CC shown not outperform consistently. present study, addition presenting novel problem, establishes useful systems further investigations correlated structure methods.

Язык: Английский

Процитировано

0