Exploring the Accuracy Limits of PNO-Based Local Coupled-Cluster Calculations for Transition-Metal Complexes

Altun, Ahmet; Riplinger, Christoph; Neese, Frank; Bistoni, Giovanni

doi:10.1021/acs.jctc.3c00087

Cited by 18 publications

(25 citation statements)

References 67 publications

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“…Similar deviations were observed for some of the extrapolated values, especially those obtained from (5/6) extrapolation (e.g., neutral Pt–CO at a multiplicity 3 with def2-SVP basis set). Again, this could be traced back to similar issues observed in the MOBH35 data set. , …”

Section: Resultssupporting

confidence: 54%

“…Again, this could be traced back to similar issues observed in the MOBH35 data set. 55,72 We have found that the proposed scheme provides a welldefined increase in the accuracy with minor dependence on the basis set size (Figure 1). This finding is of special importance because of the recently published result stating the dependence of the DLPNO error on this parameter.…”

Section: Metal−co Interactionsmentioning

confidence: 85%

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MP2-Based Correction Scheme to Approach the Limit of a Complete Pair Natural Orbitals Space in DLPNO-CCSD(T) Calculations

Pogrebetsky

Siklitskaya

Kubas

2023

J. Chem. Theory Comput.

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The domain-based local pair natural orbital (PNO) coupled-cluster DLPNO-CCSD(T) method has been proven to provide accurate single-point energies at a fraction of the cost of canonical CCSD(T) calculations. However, the desired "chemical accuracy" can only be obtained with a large PNO space and extended basis set. We present a simple yet accurate and efficient correction scheme based on a perturbative approach. Here, in addition to DLPNO-CCSD(T) energy, one calculates DLPNO-MP2 correlation energy with the same settings as in the preceding coupled-cluster calculation. In the next step, the canonical MP2 correlation energy is obtained in the same orbital basis. This can be efficiently performed for essentially all molecule sizes accessible with the DLPNO-CCSD(T) method. By taking the difference between the canonical MP2 and DLPNO-MP2 energies, we obtain a correction term that can be added to the DLPNO-CCSD(T) correlation energy. This way, one can obtain the total correlation energy close to the limit of the complete PNO space (cPNO). The presented approach allows us to significantly increase the accuracy of the DLPNO-CCSD(T) method for both closed-and open-shell systems. The latter are known to be especially challenging for locally correlated methods. Unlike the previously developed PNO extrapolation procedure by Altun, Neese, and Bistoni (J. Chem. Theory Comput. 2020, 16, 6142−6149), this strategy allows us to get the DLPNO-CCSD(T) correlation energy at the cPNO limit in a cost-efficient way, resulting in a minimal overall increase in calculation time as compared to the uncorrected method.

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Section: Resultssupporting

confidence: 54%

Section: Metal−co Interactionsmentioning

confidence: 85%

MP2-Based Correction Scheme to Approach the Limit of a Complete Pair Natural Orbitals Space in DLPNO-CCSD(T) Calculations

Pogrebetsky

Siklitskaya

Kubas

2023

J. Chem. Theory Comput.

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“…The exciting development of localized orbital approximations, such as, e.g., the PNO-LCCSD(T)-F12 and DLPNO-CCSD(T) implementations, − when appropriately converged, can also be readily used in these regimes to provide reliable reference values. With these localized coupled cluster implementations, the use of extended basis sets is possible, and thus, a more realistic evaluation of DFT methods as well as a comparison with experimentally measured ionization energies.…”

Section: Discussionmentioning

confidence: 99%

“…48,49 Later, a revision to their DLPNO-CCSD(T) references was suggested on the grounds of static correlation effects, 50 but a study by Altun et al traced the DLPNO error to correlation effects from the 3s and 3p semicore orbitals and to dynamical correlation-induced orbital relaxation effects. 51 In another study, the DLPNO approach performed well for challenging spin-splitting energies of iron complexes and reproduced CASPT2/CC results with a twopoint PNO extrapolation and improved full iterative triples. 52 Results of similar quality were found for the ionization energy of cobaltocene.…”

Section: Introductionmentioning

confidence: 86%

“…The efficiency of the DLPNO-CCSD(T) model has been demonstrated via applications to very large systems, including metalloenzymes . Iron et al used the method to compute transition metal barrier heights in the MOBH35 study. , Later, a revision to their DLPNO-CCSD(T) references was suggested on the grounds of static correlation effects, but a study by Altun et al traced the DLPNO error to correlation effects from the 3s and 3p semicore orbitals and to dynamical correlation-induced orbital relaxation effects . In another study, the DLPNO approach performed well for challenging spin-splitting energies of iron complexes and reproduced CASPT2/CC results with a two-point PNO extrapolation and improved full iterative triples .…”

Section: Introductionmentioning

confidence: 99%

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

Neugebauer,

Vuong,

Weber

et al. 2023

J. Chem. Theory Comput.

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

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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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Exploring the Accuracy Limits of PNO-Based Local Coupled-Cluster Calculations for Transition-Metal Complexes

Cited by 18 publications

References 67 publications

MP2-Based Correction Scheme to Approach the Limit of a Complete Pair Natural Orbitals Space in DLPNO-CCSD(T) Calculations

MP2-Based Correction Scheme to Approach the Limit of a Complete Pair Natural Orbitals Space in DLPNO-CCSD(T) Calculations

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

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

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