Spin-state energetics of manganese spin crossover complexes: Comparison of single-reference and multi-reference ab initio approaches

Δρόσου, Μαρία; Mitsopoulou, Christiana A.; Pantazis, Dimitrios A.

doi:10.1016/j.poly.2021.115399

Cited by 27 publications

(62 citation statements)

References 100 publications

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“…[105] Whereas CASSCF relative energies are basis set insensitive, results with correlated methods on top of CASSCF converge extremely slowly with respect to the basis set size. [69,106] The general trend is that small basis sets tend to overstabilize HS compared to LS states. It has been observed that h-type functions on the metal and f-type functions on the ligand donor atoms are essential to converge correlated relative energies to within 3 kcal/mol.…”

Section: Multireference Methodsmentioning

confidence: 99%

“…Thus, different extrapolations of local parameters have been proposed. For example, one can extrapolate to the complete PNO space using the equation E ∞ = E x + F ⋅ ( E y − E x ), where E x and E y are the correlation energies calculated with T CutPNO =10 − x and 10 − y , E ∞ is the extrapolated correlation energy at the PNO space limit, and F is a constant with the recommended value of 1.5 [68–70] …”

Section: Methodsmentioning

confidence: 99%

“…Whereas CASSCF relative energies are basis set insensitive, results with correlated methods on top of CASSCF converge extremely slowly with respect to the basis set size [69,106] . The general trend is that small basis sets tend to overstabilize HS compared to LS states.…”

Section: Methodsmentioning

confidence: 99%

“…, where E x and E y are the correlation energies calculated with T CutPNO = 10 À x and 10 À y , E ∞ is the extrapolated correlation energy at the PNO space limit, and F is a constant with the recommended value of 1.5. [68][69][70] In the case of LUCCSD(T0) calculations, errors can arise due to the domain or pair approximation. To reduce the domain error one can use explicitly correlated methods.…”

Section: Accuracy Of Coupled Cluster Approaches For Transition Metal ...mentioning

confidence: 99%

“…For example, Drousou et al employed two flavours of NEVPT2, strongly contracted (SC-NEVPT2) and fully internally contracted (FIC-NEVPT2), to investigate several manganese SCO complexes. [69] As these SCO complexes have low transition temperatures (100-300 K), the HS state is expected to be only a few kcal/mol above the LS GS. Out of eight Mn complexes, FIC-NEVPT2 fails to predict the correct GS of three complexes, i. e., the HS-LS gaps are negative.…”

Section: Spin State Energetics In Spin-crossover Compoundsmentioning

confidence: 99%

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Ab Initio Methods in First‐Row Transition Metal Chemistry

Feldt

Phung

2022

Eur J Inorg Chem

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Molecules containing 3d transition metals (TMs) are usually associated with versatile reactivity, partly due to their complicated electronic structures involving multiple close‐lying spin states. An accurate description of different electronic states is notoriously difficult and still a challenge for computational methodologies. Density functional theory, although repeatedly shown to give less reliable results for near‐degeneracy problems, remains the workhorse to explore the reactivity of TM complexes. Ab initio wavefunction theory has been lagging behind due to its high computational cost. However, tremendous efforts have been put to improve their applicability over the past few years, particularly local coupled cluster and low‐scaling multireference methods. In this mini‐review, we highlight major advancements of these ab initio techniques and discuss their recent applications in the calculations of spin state energetics of first‐row TM complexes, ranging from spin crossover compounds and metalloproteins to biomimetic complexes capable of activating C−H bonds.

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Section: Multireference Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Accuracy Of Coupled Cluster Approaches For Transition Metal ...mentioning

confidence: 99%

Section: Spin State Energetics In Spin-crossover Compoundsmentioning

confidence: 99%

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Ab Initio Methods in First‐Row Transition Metal Chemistry

Feldt

Phung

2022

Eur J Inorg Chem

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Another Torture Track for Quantum Chemistry: Reinvestigation of the Benzaldehyde Amidation by Nitrogen‐Atom Transfer from Platinum(II) and Palladium(II) Metallonitrenes

Verplancke

Diefenbach

Lienert

et al. 2023

Israel Journal of Chemistry

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We showcase here a dramatic failure of CCSD(T) theory that originates from the pronounced multi‐reference character of a key intermediate formed in the benzaldehyde amidation by N‐atom transfer from Pd(II) and Pt(II) metallonitrenes studied recently in combined experimental and theoretical work. For detailed analysis we devised a minimal model system, for which we established reliable reference energies based on approximate full configuration interaction theory, to assess the performance of single‐reference coupled‐cluster theory up to the CCSDTQ(P) excitation level. While RHF‐based CCSD(T) theory suffered dramatic errors, in one case exceeding 220 kcal mol−1, we show that the use of broken‐symmetry (BS) or Kohn‐Sham (KS) orbital references yields substantially improved CCSD(T) results. Further, the EOM‐SF‐CCSD(T)(a)* approach met the reference data with excellent accuracy. We applied the KS‐CCSD(T*)‐F12b variant as high‐level part of an ONIOM(KS‐CC:DFT) scheme to reinvestigate the reactivity of the full Pt(II) and Pd(II) metallonitrenes. The revised reaction pathway energetics provide a detailed mechanistic rationale for the experimental observations.

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Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes

Chamkin,

Chamkina

2024

J Comput Chem

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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 of 26 elementary reactions featuring chemical transformations and bonding situations essential for the field, including the emerging concept of non‐innocent Cp* behavior. Reference values were obtained from a highly accurate 3/4 complete basis set and 6/7 complete PNO space extrapolated DLPNO‐CCSD(T) energies. The performance of lower‐level extrapolation procedures was also assessed. We considered 84 density functionals (DF) (including 13 generalized gradient approximations (GGA), nine meta‐GGAs, 33 hybrids, and 29 double‐hybrids) and three composite methods (HF‐3c, PBEh‐3c, and r2SCAN‐3c), combined with different types of dispersion corrections (D3(0), D3BJ, D4, and VV10). The most accurate approach is the PBE0‐DH‐D3BJ (MAD of 1.36 kcal mol−1) followed by TPSS0‐D3BJ (MAD of 1.60 kcal mol−1). Low‐cost r2SCAN‐3c composite provides a less accurate but much faster alternative (MAD of 2.39 kcal mol−1). The widely used Minnesota‐family M06‐L, M06, and M06‐2X DFs should be avoided (MADs of 3.70, 3.94, and 4.01 kcal mol−1, respectively).

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Spin-state energetics of manganese spin crossover complexes: Comparison of single-reference and multi-reference ab initio approaches

Cited by 27 publications

References 100 publications

Ab Initio Methods in First‐Row Transition Metal Chemistry

Ab Initio Methods in First‐Row Transition Metal Chemistry

Another Torture Track for Quantum Chemistry: Reinvestigation of the Benzaldehyde Amidation by Nitrogen‐Atom Transfer from Platinum(II) and Palladium(II) Metallonitrenes

Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes

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