Assessment of density functionals and paucity of non-covalent interactions in aminoylyne complexes of molybdenum and tungsten [(η5-C5H5)(CO)2MEN(SiMe3)(R)] (E = Si, Ge, Sn, Pb): a dispersion-corrected DFT study

Pandey, Krishna K.; Patidar, Pankaj; Bariya, Pankaj K.; Patidar, Sunil K.; Vishwakarma, Ravi

doi:10.1039/c3dt53632g

Cited by 12 publications

(12 citation statements)

References 76 publications

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“…The Grimme's D3(BJ) dispersion correction 72 was applied to arrive at the PBE0-D3(BJ) functional, to account for the possible influence of dispersion interactions on molecular geometries. [97][98][99] Default values were adopted to control the convergence of the SCF iterative steps. Tighter than default, "tight" criteria have been used for geometry optimization: maximum force = 1.5 10 -5 a.u., RMS force = 1.0 10 -5 a.u., maximum displacement = 6.0 10 -5 Å, and RMS displacement = 4.0 10 -5 Å.…”

Section: Geometry Optimizationmentioning

confidence: 99%

Heats of Formation of Medium-Sized Organic Compounds from Contemporary Electronic Structure Methods

Minenkov

Wang

et al. 2017

J. Chem. Theory Comput.

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Computational electronic structure calculations are routinely undertaken to predict thermodynamic properties of various species. However, the application of highly accurate wave function theory methods, such as the "gold standard" coupled cluster approach including single, double, and partly triple excitations in perturbative fashion, CCSD(T), to large molecules is limited due to high computational cost. In this work, the promising domain based local pair natural orbital coupled cluster approach, DLPNO-CCSD(T), has been tested to reproduce 113 accurate formation enthalpies of medium-sized molecules (few dozens heavy atoms) important for bio- and combustion chemistry via the reaction based Feller-Peterson-Dixon approach. For comparison, eight density functional theory (B3LYP, B3LYP-D3, PBE0, PBE0-D3, M06, M06-2X, ωB97X-D3, and ωB97M-V) and MP2-based (B2PLYP-D3, PWPB95-D3, B2T-PLYP, B2T-PLYP-D, B2GP-PLYP, DSD-PBEP86-D3, SCS-MP2, and OO-SCS-MP2) methods have been tested. The worst performance has been obtained for the standard hybrid DFT functionals, PBE0 (mean unsigned error (MUE)/mean signed error (MSE) = 9.1/6.0 kcal/mol) and B3LYP (MUE/MSE = 13.5/-13.3 kcal/mol). The influence of an empirical dispersion correction term on these functionals' performance is not homogeneous: B3LYP performance is improved (B3LYP-D3 (MUE/MSE = 6.0/0.8 kcal/mol)); meanwhile PBE0 performance is worse (PBE0-D3 (MUE/MSE = 14.1/13.6 kcal/mol)). The Minnesota functionals, M06 (MUE/MSE = 3.8/-2.0 kcal/mol) and M06-2X (MUE/MSE = 3.5/3.0 kcal/mol), and recently developed ωB97X-D3 (MUE/MSE = 3.2/0.2 kcal/mol) and ωB97M-V (MUE/MSE = 2.2/1.3 kcal/mol) methods provided significantly better formation enthalpies. Enthalpies of similar quality can also be obtained from some double hybrid methods (B2PLYP-D3 (MUE/MSE = 4.7/2.0 kcal/mol), PWPB95-D3 (MUE/MSE = 4.3/3.2 kcal/mol), B2T-PLYP (MUE/MSE = 4.1/-3.0 kcal/mol), and B2T-PLYP-D (MUE/MSE = 3.3/1.7 kcal/mol)). The two spin component scaled (SCS) MP2 methods resulted in even smaller errors (SCS-MP2 (MUE/MSE = 1.9/1.2 kcal/mol) and OO-SCS-MP2 (MUE/MSE = 1.6/0.1 kcal/mol)). The best performance was found for the frozen core (FC) DLPNO-CCSD(T) method with a MUE/MSE of 1.6/-1.2 kcal/mol. The performance of the DLPNO-CCSD(T) method can be further improved by running the post-SCF calculations on the B3LYP orbitals: the MUE/MSE for the DLPNO-CCSD(T,B3LYP) approximation is 1.2/-0.4 kcal/mol. We recommend the DLPNO-CCSD(T,B3LYP) method for black box applications in thermodynamics of medium-sized organic molecules when the canonical CCSD(T) calculations with basis sets of reasonable quality are prohibitively expensive.

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Section: Geometry Optimizationmentioning

confidence: 99%

Heats of Formation of Medium-Sized Organic Compounds from Contemporary Electronic Structure Methods

Minenkov

Wang

et al. 2017

J. Chem. Theory Comput.

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“…A similar time-delayed history exists for the experimental attempts to synthesis the heavy group-14 homologues of transition metal carbyne complexes. 84 Following the first synthesis of a carbyne complex by Fischer in 1973, 59 the next member in the series which could become characterized by X-ray analysis was a germylyne complex which was reported by Power in 1996. 85 The other three members of the group of heavier carbyne homologues for which X-ray structure analyses have been synthesized by Filippou.…”

Section: Transition Metal-tetrele Complexes [Tm]-e (E = Si Ge Sn)mentioning

confidence: 99%

New bonding modes of carbon and heavier group 14 atoms Si–Pb

et al. 2014

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Recent theoretical studies are reviewed which show that the naked group 14 atoms E = C-Pb in the singlet (1)D state behave as bidentate Lewis acids that strongly bind two σ donor ligands L in the donor-acceptor complexes L→E←L. Tetrylones EL2 are divalent E(0) compounds which possess two lone pairs at E. The unique electronic structure of tetrylones (carbones, silylones, germylones, stannylones, plumbylones) clearly distinguishes them from tetrylenes ER2 (carbenes, silylenes, germylenes, stannylenes, plumbylenes) which have electron-sharing bonds R-E-R and only one lone pair at atom E. The different electronic structures of tetrylones and tetrylenes are revealed by charge- and energy decomposition analyses and they become obvious experimentally by a distinctively different chemical reactivity. The unusual structures and chemical behaviour of tetrylones EL2 can be understood in terms of the donor-acceptor interactions L→E←L. Tetrylones are potential donor ligands in main group compounds and transition metal complexes which are experimentally not yet known. The review also introduces theoretical studies of transition metal complexes [TM]-E which carry naked tetrele atoms E = C-Sn as ligands. The bonding analyses suggest that the group-14 atoms bind in the (3)P reference state to the transition metal in a combination of σ and π∥ electron-sharing bonds TM-E and π⊥ backdonation TM→E. The unique bonding situation of the tetrele complexes [TM]-E makes them suitable ligands in adducts with Lewis acids. Theoretical studies of [TM]-E→W(CO)5 predict that such species may becomes synthesized.

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“…34, 128-132 The Grimme's D3(BJ) 118 dispersion correction was applied to arrive at the PBE-D3(BJ) functional, to account the possible influence of the noncovalent interaction not covered by standard PBE functional on molecular geometries. [133][134][135] The default values were adopted for the self-consistent-field (SCF) and geometry optimization convergence criteria. Numerical integration of the exchange-correlation (XC) terms was performed using tighter-than-default "ultrafine" option (pruned, 99 radial shells and 590 angular points per shell) to eliminate the potential numerical noise in energy second derivatives.…”

Section: Introductionmentioning

confidence: 99%

Application of Semiempirical Methods to Transition Metal Complexes: Fast Results but Hard-to-Predict Accuracy

Minenkov

Sharapa

Cavallo

2018

J. Chem. Theory Comput.

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A series of semiempirical PM6* and PM7 methods has been tested in reproducing relative conformational energies of 27 realistic-size complexes of 16 different transition metals (TMs). An analysis of relative energies derived from single-point energy evaluations on density functional theory (DFT) optimized conformers revealed pronounced deviations between semiempirical and DFT methods, indicating a fundamental difference in potential energy surfaces (PES). To identify the origin of the deviation, we compared fully optimized PM7 and respective DFT conformers. For many complexes, differences in PM7 and DFT conformational energies have been confirmed often manifesting themselves in false coordination of some atoms (H, O) to TMs and chemical transformations/distortion of coordination center geometry in PM7 structures. Despite geometry optimization with fixed coordination center geometry leading to some improvements in conformational energies, the resulting accuracy is still too low to recommend explored semiempirical methods for out-of-the-box conformational search/sampling: careful testing is always needed.

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Assessment of density functionals and paucity of non-covalent interactions in aminoylyne complexes of molybdenum and tungsten [(η⁵-C₅H₅)(CO)₂MEN(SiMe₃)(R)] (E = Si, Ge, Sn, Pb): a dispersion-corrected DFT study

Cited by 12 publications

References 76 publications

Heats of Formation of Medium-Sized Organic Compounds from Contemporary Electronic Structure Methods

Heats of Formation of Medium-Sized Organic Compounds from Contemporary Electronic Structure Methods

New bonding modes of carbon and heavier group 14 atoms Si–Pb

Application of Semiempirical Methods to Transition Metal Complexes: Fast Results but Hard-to-Predict Accuracy

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