Do Double-Hybrid Exchange–Correlation Functionals Provide Accurate Chemical Shifts? A Benchmark Assessment for Proton NMR

Oliveira, Marcelo Tavares de; Alves, Júlia Maria Aragon; Braga, Ataualpa Albert Carmo; Wilson, David J.; Barboza, Cristina A.

doi:10.1021/acs.jctc.1c00604

Cited by 50 publications

(33 citation statements)

References 99 publications

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“…Currently, it appears that the shieldings of main-group systems, on which we concentrate in this work, are best reproduced by some so-called double-hybrid functionals (DHs) on the fifth rung of Perdew’s ladder of XC functionals, in particular, the DSD-PBEP86 functional , based on spin-component-scaled (SCS) MP2 (a recent comparison with experimental 1 H shifts comes to a different conclusion but suffers from methodological inadequacies). The nonlocal MP2-type correlation of DHs in conjunction with GIAOs introduces substantial computational demands (estimated to be 1–2 orders of magnitude larger than a regular DFT shielding calculation), however, placing this class of functionals in an accuracy and cost range intermediate between the more standard DFT approaches and the CCSD(T) reference method.…”

Section: Introductionmentioning

confidence: 99%

Extended Benchmark Set of Main-Group Nuclear Shielding Constants and NMR Chemical Shifts and Its Use to Evaluate Modern DFT Methods

Schattenberg

Kaupp

2021

J. Chem. Theory Comput.

141

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An extended theoretical benchmark set, NS372, for light main-group nuclear shieldings and NMR shifts has been constructed based on high-level GIAO-CCSD(T)/pcSseg-3//CCSD(T)/cc-pVQZ reference data. After removal of the large static-correlation cases O3, F3 –, and BH from the statistical evaluations for the 17O, 19F, and 11B subsets, the benchmark comprises overall 372 shielding values in 117 molecules with a wide range of electronic-structure situations, containing 124 1H, 14 11B, 93 13C, 43 15N, 31 17O, 47 19F, 14 31P, and 6 33S shielding constants. The CCSD(T)/pcSseg-3 data are shown to be close to the basis-set and method limit and thus provide an excellent benchmark to evaluate more approximate methods, such as density functional approaches. This dataset has been used to evaluate Hartree–Fock (HF) and MP2, and a wide range of exchange–correlation functionals from local density approximation (LDA) to generalized gradient approximations (GGAs) and meta-GGAs (focusing on their current-density functional implementations), as well as global hybrid, range-separated hybrid, local hybrid, and double-hybrid functionals. Starting with absolute shielding constants, the DSD-PBEP86 double hybrid is confirmed to provide the highest accuracy, with an aggregate relative mean absolute error (rel. MAE) of only 0.9%, followed by MP2 (1.1%). MP2 and double hybrids only show larger errors for a few systems with the largest static-correlation effects. The double-hybrid B2GP-PLYP, the two local hybrids cLH12ct-SsirPW92 and cLH12ct-SsifPW92, and the current-density functional meta-GGA cB97M-V follow closely behind (all 1.5%), as do some further functionals, cLH20t and cMN15-L (both 1.6%), as well as B2PLYP and KT3 (both 2.0%). Functionals on the lower rungs of the usual ladder offer the advantage of lower computational cost and access to larger molecules. Closer examination also reveals the best-performing methods for individual nuclei in the test set. Different ways of treating τ-dependent functionals are evaluated. When moving from absolute shielding constants to chemical shifts, some of the methods can benefit from systematic error compensation, and the overall error range somewhat narrows. Further methods now achieve the 2% threshold of relative MAEs, including functionals based on TPSS (TPSSh, cmPSTS).

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Section: Introductionmentioning

confidence: 99%

Extended Benchmark Set of Main-Group Nuclear Shielding Constants and NMR Chemical Shifts and Its Use to Evaluate Modern DFT Methods

Schattenberg

Kaupp

2021

J. Chem. Theory Comput.

141

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“…4, were calculated based on the gauge-independent atomic orbital (GIAO) method at the mPW1PW91/6-31 + G(d) and revTPSS/pcSseg-1 level (Table S5 †). 19 The calculated NMR chemical shifts for 1a possessed lower mean absolute error (MAE) and maximum deviation (MD) than 1b, especially when comparing the data of the carbons next to the pending chiral center (C-7, C-8, C-9, and C-14), the tendency of 1a is more pronounced. Nevertheless, 1a was proven to have a DP4+ possibility of 100% against its isomer 1b, 20,21 suggesting 1a to be the correct structure.…”

Section: Resultsmentioning

confidence: 92%

Unprecedented diterpenoid dimers with soluble epoxide hydrolase inhibitory effect from Euphorbia fischeriana

et al. 2022

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“…The occurring conformers of 14 were then subjected to NMR shielding constants calculation using the gauge-independent atomic orbitals (GIAO) method at the revtpssrevtpss/pcSseg-1/(PCM, methanol) level. [33,34] The optical rotation values for conformers of 1, 2 and 14 were calculated at cam-B3LYP/ aug-cc-pVTZ/(PCM, methanol) level. [35] The calculated NMR and optical rotation properties were averaged based on the Boltzmann populations of all conformers, and the overall theoretical NMR data were analyzed using DP4 + probability.…”

Section: Data Processingmentioning

confidence: 99%

New Cytotoxic Secondary Metabolites from Two Deep‐Sea‐Derived Fungi and the Co‐Culture Impact on the Secondary Metabolic Patterns

et al. 2022

Chemistry & Biodiversity

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In this study, chemical profiles for two co‐existing deep‐sea‐derived Penicillium fungal strains were thoroughly investigated. Two new compounds and 11 known compounds were identified from Penicillium sp. LXY140‐R, while one new compound and 12 known compounds were isolated from Penicillium sp. LXY140‐3. Their structures were elucidated by extensive 1D and 2D NMR experiments, which were supported by HR‐ESI‐MS data. The antiproliferative activities of all isolates against HCT‐116, A549 and Bel‐7402 cell lines were also evaluated. Compounds 2, 5, 6, 10 and 13 showed potent antiproliferative activity. To reveal the metabolic relationship of the two strains, we conducted co‐culture experiments to discover cross‐talk molecules by a device that allows only small molecule to communicate. Extensive HPLC/MS2 experiments were applied to identify the disturbance of the chemical profiles within the synthetic Penicillium‐Penicillium community. The fungal strain LXY140‐R was found to accumulate mono or multiple‐acetylation derivatives of deoxynivalenol (DON) sesquiterpenes as responsible molecules by the disturbance of the metabolites produced by the LXY140‐3 strain.

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Do Double-Hybrid Exchange–Correlation Functionals Provide Accurate Chemical Shifts? A Benchmark Assessment for Proton NMR

Cited by 50 publications

References 99 publications

Extended Benchmark Set of Main-Group Nuclear Shielding Constants and NMR Chemical Shifts and Its Use to Evaluate Modern DFT Methods

Extended Benchmark Set of Main-Group Nuclear Shielding Constants and NMR Chemical Shifts and Its Use to Evaluate Modern DFT Methods

Unprecedented diterpenoid dimers with soluble epoxide hydrolase inhibitory effect from Euphorbia fischeriana

New Cytotoxic Secondary Metabolites from Two Deep‐Sea‐Derived Fungi and the Co‐Culture Impact on the Secondary Metabolic Patterns

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