Toward Benchmark-quality Ab Initio Predictions for 3d Transition Metal Electrocatalysts - A Comparison of CCSD(T) and ph-AFQMC DOI Creative Commons
Hagen Neugebauer,

Hung Vuong,

John L. Weber

и другие.

Опубликована: Авг. 17, 2023

Generating accurate ab initio ionization energies for transition metal complexes is an important step towards the computational description of their electrocatalytic reactions. Benchmark-quality data required testing existing theoretical methods and developing new ones but complicated to obtain many compounds due potential presence both strong dynamical static electron correlation. In this regime, it questionable whether so-called gold standard, coupled cluster with singles, doubles, perturbative triples (CCSD(T)), provides desired level accuracy -- roughly 1-3 kcal/mol. work, we compiled a test set 28 3d metal-containing molecules relevant homogeneous electrocatalysis (termed 3dTMV) computed vertical (ionization potentials) CCSD(T) phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) in def2-SVP basis set. A substantial effort has been made converge away bias ph-AFQMC reference values. We assess wide variety multireference diagnostics, find that spin-symmetry breaking CCSD wavefunction PBE0 density functional correlate well our analysis multiconfigurational wavefunctions. propose quantitative criteria based on symmetry delineate correlation regimes inside which appropriately-performed can produce mean absolute deviations from values 2 kcal/mol or less, outside expected fail. also present preliminary assessment DFT functionals 3dTMV

Язык: Английский

Toward Benchmark-Quality Ab Initio Predictions for 3d Transition Metal Electrocatalysts: A Comparison of CCSD(T) and ph-AFQMC DOI
Hagen Neugebauer,

Hung Vuong,

John L. Weber

и другие.

Journal of Chemical Theory and Computation, Год журнала: 2023, Номер 19(18), С. 6208 - 6225

Опубликована: Сен. 1, 2023

Generating accurate ab initio ionization energies for transition metal complexes is an important step toward the computational description of their electrocatalytic reactions. Benchmark-quality data required testing existing theoretical methods and developing new ones but complicated to obtain many compounds due potential presence both strong dynamical static electron correlation. In this regime, it questionable whether so-called gold standard, coupled cluster with singles, doubles, perturbative triples (CCSD(T)), provides desired level accuracy─roughly 1-3 kcal/mol. work, we compiled a test set 28 3d metal-containing molecules relevant homogeneous electrocatalysis (termed 3dTMV) computed vertical (ionization potentials) CCSD(T) phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) in def2-SVP basis set. A substantial effort has been made converge away bias ph-AFQMC reference values. We assess wide variety multireference diagnostics find that spin-symmetry breaking CCSD wave function PBE0 density functional correlate well our analysis multiconfigurational functions. propose quantitative criteria based on symmetry delineate correlation regimes inside which appropriately performed can produce mean absolute deviations from values roughly 2 kcal/mol or less outside expected fail. also present preliminary assessment theory (DFT) functionals 3dTMV

Язык: Английский

Процитировано

15
Synthetic and Mechanistic Studies into the Reductive Functionalization of Nitro Compounds Catalyzed by an Iron(salen) Complex DOI Creative Commons

Emily Pocock,

Martin Diefenbach, Thomas M. Hood

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 19839 - 19851

Опубликована: Июль 12, 2024

We report on the use of a simple, bench-stable [Fe(salen)2]-μ-oxo precatalyst in reduction nitro compounds. The reaction proceeds at room temperature across range substrates, including aromatics and aliphatics. By changing reducing agent from pinacol borane (HBpin) to phenyl silane (H3SiPh), we can chemoselectively reduce compounds while retaining carbonyl functionality. Our mechanistic studies, which include kinetics, electron paramagnetic resonance (EPR), mass spectrometry, quantum chemistry, indicate presence nitroso intermediate generation an on-cycle iron hydride as key catalytic intermediate. Based this insight, were able extend chemistry hydroamination identified simple substrate feature (alkene lowest unoccupied molecular orbital (LUMO) energy) that could be used predict alkenes would result productive catalysis.

Язык: Английский

Процитировано

4
C═C Dissociative Imination of Styrenes by a Photogenerated Metallonitrene DOI Creative Commons
Till Schmidt‐Räntsch, Hendrik Verplancke, Annemarie Kehl

и другие.

JACS Au, Год журнала: 2024, Номер 4(9), С. 3421 - 3426

Опубликована: Сен. 3, 2024

Photolysis of a platinum(II) azide complex in the presence styrenes enables C=C double bond cleavage upon dissociative olefin imination to aldimido (Pt

Язык: Английский

Процитировано

2
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
Toward Benchmark-quality Ab Initio Predictions for 3d Transition Metal Electrocatalysts - A Comparison of CCSD(T) and ph-AFQMC DOI Creative Commons
Hagen Neugebauer,

Hung Vuong,

John L. Weber

и другие.

Опубликована: Июнь 9, 2023

Generating accurate ab initio ionization energies for transition metal complexes is an important step towards the computational description of their electrocatalytic reactions. Benchmark-quality data required testing existing theoretical methods and developing new ones but complicated to obtain many compounds due potential presence both strong dynamical static electron correlation. In this regime, it questionable whether so-called gold standard, coupled cluster with singles, doubles, perturbative triples (CCSD(T)), provides desired level accuracy -- roughly 1-3 kcal/mol. work, we compiled a test set 28 3d metal-containing molecules relevant homogeneous electrocatalysis (termed 3dTMV) computed vertical (ionization potentials) CCSD(T) phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC). A substantial effort has been made converge away bias in ph-AFQMC reference values. We assess wide variety multireference diagnostics, find that spin-symmetry breaking CCSD wavefunction PBE0 density functional correlate well our analysis multiconfigurational wavefunctions. propose quantitative criteria based on symmetry delineate correlation regimes inside which appropriately-performed can produce mean absolute deviations from values 2 kcal/mol or less, outside expected fail. also present preliminary assessment DFT functionals 3dTMV set.

Язык: Английский

Процитировано

3
Toward Benchmark-quality Ab Initio Predictions for 3d Transition Metal Electrocatalysts - A Comparison of CCSD(T) and ph-AFQMC DOI Creative Commons
Hagen Neugebauer,

Hung Vuong,

John L. Weber

и другие.

Опубликована: Авг. 17, 2023

Generating accurate ab initio ionization energies for transition metal complexes is an important step towards the computational description of their electrocatalytic reactions. Benchmark-quality data required testing existing theoretical methods and developing new ones but complicated to obtain many compounds due potential presence both strong dynamical static electron correlation. In this regime, it questionable whether so-called gold standard, coupled cluster with singles, doubles, perturbative triples (CCSD(T)), provides desired level accuracy -- roughly 1-3 kcal/mol. work, we compiled a test set 28 3d metal-containing molecules relevant homogeneous electrocatalysis (termed 3dTMV) computed vertical (ionization potentials) CCSD(T) phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) in def2-SVP basis set. A substantial effort has been made converge away bias ph-AFQMC reference values. We assess wide variety multireference diagnostics, find that spin-symmetry breaking CCSD wavefunction PBE0 density functional correlate well our analysis multiconfigurational wavefunctions. propose quantitative criteria based on symmetry delineate correlation regimes inside which appropriately-performed can produce mean absolute deviations from values 2 kcal/mol or less, outside expected fail. also present preliminary assessment DFT functionals 3dTMV

Язык: Английский

Процитировано

3