Auxiliary basis sets for density-fitting second-order Møller-Plesset perturbation theory: Weighted core-valence correlation consistent basis sets for the 4<i>d</i>elements Y-Pd

Hill, Jimmy

doi:10.1002/jcc.23372

Cited by 11 publications

(14 citation statements)

References 56 publications

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“…For a basis set, the outer core-valence correlation correction for activation energy is obtained by subtracting the barrier without core-valence correlation from the barrier with core-valence correlation, both calculated with the same basis set. The results in Table 2 show that the core-valence 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 of the other two-electron integral and resolution of the identity approximation employed cc-pwCVTZ-PP/MP2FIT 182,187 for Mo/W and cc-pVTZ/MP2FIT for the rest atoms.…”

Section: ) From Ccsd(t) and Ccsd(t)-f12bmentioning

confidence: 99%

Assessment of DFT Methods for Computing Activation Energies of Mo/W-Mediated Reactions

Chen

2015

J. Chem. Theory Comput.

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Using high level ab initio coupled cluster calculations as reference, the performances of 15 commonly used density functionals (DFs) on activation energy calculations for typical Mo/W-mediated reactions have been systematically assessed for the first time in this work. The selected representative Mo/W-mediated reactions cover a wide range from enzymatic reactions to organometallic reactions, which include Mo-catalyzed aldehyde oxidation (aldehyde oxidoreductase), Mo-catalyzed dimethyl sulfoxide (DMSO) reduction (DMSO reductase), W-catalyzed acetylene hydration (acetylene hydratase), Mo/W-mediated olefin metathesis, Mo/W-mediated olefin epoxidation, W-mediated alkyne metathesis, and W-mediated C-H bond activation. Covering both Mo- and W-mediated reactions, four DFs of B2GP-PLYP, M06, B2-PLYP, and B3LYP are uniformly recommended with and without DFT empirical dispersion correction. Among these four DFs, B3LYP is notably improved in performance by DFT empirical dispersion correction. In addition to the absolute value of calculation error, if the trend of DFT results is also a consideration, B2GP-PLYP, B2-PLYP, and M06 keep better performance than other functionals tested and constitute our final recommendation of DFs for both Mo- and W-mediated reactions.

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Section: ) From Ccsd(t) and Ccsd(t)-f12bmentioning

confidence: 99%

Assessment of DFT Methods for Computing Activation Energies of Mo/W-Mediated Reactions

Chen

2015

J. Chem. Theory Comput.

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“…These differences lie in the fact that in core−valence electron correlation calculations (a) all diffuse auxiliary bases were not included; and that (b) cc-pwCVTZ-PP/MP2FIT instead of aug-cc-pVTZ-PP/MP2FIT was used for Ru and Rh. 119 Considering both the valence-only electron correlation and the Ru/Rh 4s4p outer core−valence electron correlation, the final reference values of activation energies and reaction energies can be written as…”

Section: Computational Detailsmentioning

confidence: 99%

Comparative Assessment of DFT Performances in Ru- and Rh-Promoted σ-Bond Activations

Sun

Chen

2015

J. Chem. Theory Comput.

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In this work, the performances of 19 density functional theory (DFT) methods are calibrated comparatively on Ru-and Rh-promoted σ-bond (C−H, O−H, and H−H) activations. DFT calibration reference is generated from explicitly correlated coupled cluster CCSD(T)-F12 calculations, and the 4s4p core−valence correlation effect of the two 4d platinum group transition metals is also included. Generally, the errors of DFT methods for calculating energetics of Ru-/Rh-mediated reactions appear to correlate more with the magnitude of energetics itself than other factors such as metal identity. For activation energy calculations, the best performing functionals for both Ru and Rh systems are MN12SX < CAM-B3LYP < M06-L < MN12L < M06 < ωB97X < B3LYP < LC-ωPBE (in the order of increasing mean unsigned deviations, MUDs, of less than 2 kcal/mol). For reaction energy calculations, best functionals with MUDs less than 2 kcal/mol are PBE0 < CAM-B3LYP ≈ N12SX. The effect of the DFT empirical dispersion correction on the performance of the DFT methods is beneficial for most density functionals tested in this work, reducing their MUDs to different extents. After including empirical dispersion correction, ωB97XD, B3LYP-D3, and CAM-B3LYP-D3 (PBE0-D3, B3LYP-D3, and ωB97XD) are the three best performing DFs for activation energy (reaction energy) calculations, from which B3LYP-D3 and ωB97XD can notably be recommended uniformly for both the reaction energy and reaction barrier calculations. The good performance of B3LYP-D3 in quantitative description of the energetic trends further adds value to B3LYP-D3 and singles this functional out as a reasonable choice in the Ru/Rh-promoted σ-bond activation processes.

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“…The optimized auxiliary basis sets have been reported in a series of papers. [15][16][17][18][19][20][21][22][23][24][25] Following the earlier reports, we optimized the auxiliary basis sets by minimizing the functional…”

Section: Optimization Of the Auxiliary Basis Setsmentioning

confidence: 99%

Development of new auxiliary basis functions of the Karlsruhe segmented contracted basis sets including diffuse basis functions (def2-SVPD, def2-TZVPPD, and def2-QVPPD) for RI-MP2 and RI-CC calculations

Hellweg

Rappoport

2015

Phys. Chem. Chem. Phys.

136

120

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We report optimized auxiliary basis sets for use with the Karlsruhe segmented contracted basis sets including moderately diffuse basis functions (Rappoport and Furche, J. Chem. Phys., 2010, 133, 134105) in resolution-of-the-identity (RI) post-self-consistent field (post-SCF) computations for the elements H-Rn (except lanthanides). The errors of the RI approximation using optimized auxiliary basis sets are analyzed on a comprehensive test set of molecules containing the most common oxidation states of each element and do not exceed those of the corresponding unaugmented basis sets. During these studies an unsatisfying performance of the def2-SVP and def2-QZVPP auxiliary basis sets for Barium was found and improved sets are provided. We establish the versatility of the def2-SVPD, def2-TZVPPD, and def2-QZVPPD basis sets for RI-MP2 and RI-CC (coupled-cluster) energy and property calculations. The influence of diffuse basis functions on correlation energy, basis set superposition error, atomic electron affinity, dipole moments, and computational timings is evaluated at different levels of theory using benchmark sets and showcase examples.

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Auxiliary basis sets for density-fitting second-order Møller-Plesset perturbation theory: Weighted core-valence correlation consistent basis sets for the 4delements Y-Pd

Cited by 11 publications

References 56 publications

Assessment of DFT Methods for Computing Activation Energies of Mo/W-Mediated Reactions

Assessment of DFT Methods for Computing Activation Energies of Mo/W-Mediated Reactions

Comparative Assessment of DFT Performances in Ru- and Rh-Promoted σ-Bond Activations

Development of new auxiliary basis functions of the Karlsruhe segmented contracted basis sets including diffuse basis functions (def2-SVPD, def2-TZVPPD, and def2-QVPPD) for RI-MP2 and RI-CC calculations

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