Many Density Functional Theory Approaches Fail To Give Reliable Large Hydrocarbon Isomer Energy Differences

Schreiner, Peter R.; Fokin, Andrey A.; Pascal, and Robert A.; Meijere, Armin de

doi:10.1021/ol0610486

Cited by 313 publications

(281 citation statements)

References 16 publications

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“…These and similar examples have recently attracted a lot of attention in the theoretical community [126][127][128][129][130][131][132][133][134][135][136] although, from the very beginning, the DH forms were announced as the way to go in the future [137,138]; more discussion can be found in the series of last annual reviews highlighting achievements in computational organic chemistry [139][140][141].…”

Section: Self-interaction Errormentioning

confidence: 99%

Double-hybrid density functionals: merging wavefunction and density approaches to get the best of both worlds

Sancho‐García

Adamo

2013

Phys. Chem. Chem. Phys.

109

108

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We review in this Perspective why and how double-hybrid density functionals have become new leading actors in the field of computational chemistry, thanks to the combination of an unprecedented accuracy together with large robustness and reliability. Similarly to their predecessors, the widely employed hybrid density functionals, they are rooted on the Adiabatic Connection Method from which they emerge in a natural way. We present recent achievements concerning applications to chemical systems of the most interest, and current extensions to deal with challenging issues such as non-covalent interactions and excitation energies. These promising methods, despite a slightly higher computational cost than other typical density-based models, are called to play a key role in the near future and can thus pave the way towards new discoveries or advances.2

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Section: Self-interaction Errormentioning

confidence: 99%

Double-hybrid density functionals: merging wavefunction and density approaches to get the best of both worlds

Sancho‐García

Adamo

2013

Phys. Chem. Chem. Phys.

109

108

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“…The M062X functional appears to offer comparable isomerization energy prediction performance to the best performing currently available dispersion corrected functionals against this benchmark dataset.The performance of various levels of quantum chemical methods for estimating the isomerization energies (∆ isom E) and enthalpies (∆ isom H) of organic compounds has been the focus of a number of investigations over the past several years [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. This attention is primarily driven by the poor performance of many popular density functionals -most notably the B3LYP functional -with regard to these types of intramolecular rearrangements.…”

mentioning

confidence: 99%

Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules

Rayne

Forest

2010

Nat Prec

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Gas phase standard state (298.15 K, 1 atm) isomerization energies (∆ isom E) were calculated using the M062X functional with the QZVP, 6-311++G(d,p), 6-311++G(2d,2p), and cc-pVTZ basis sets against the 24 reactions in the ISOL set of benchmark isomerization energies for large organic molecules. The M062X functional appears to offer comparable isomerization energy prediction performance to the best performing currently available dispersion corrected functionals against this benchmark dataset.The performance of various levels of quantum chemical methods for estimating the isomerization energies (∆ isom E) and enthalpies (∆ isom H) of organic compounds has been the focus of a number of investigations over the past several years [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. This attention is primarily driven by the poor performance of many popular density functionals -most notably the B3LYP functional -with regard to these types of intramolecular rearrangements. Several new types of functionals and corrections have been developed in response to these reported theoretical shortcomings. However, prior ∆ isom H/∆ isom E benchmarking efforts have concentrated on relatively small molecules (<8 heavy atoms).Recently, Huenerbein et al. [15] have proposed the ISOL set of 24 isomerization reactions for large organic compounds (Figure 1). In their benchmarking study, the authors obtained reference ∆ isom E at the SCS-MP3/CBS level on B97D/TZVP optimized structures. Based on previous efforts showing the M062X density functional performs well for computing ∆ isom H/∆ isom E of smaller organic molecules [6,[10][11][12], in the current work we assess the performance of this functional for calculating ∆ isom E for the ISOL benchmark set.Single point calculations were performed using Gaussian 09 [16] and the M062X density functional [17] with the QZVP [18], 6-311++G(d,p) and 6-311++G(2d,2p) [19][20][21][22][23], and cc-pVTZ [24,25] basis sets on the B97D/TZVP optimized geometries from the ISOL set in Huenerbein et al. [15], and corresponding ∆ isom E were calculated along with associated method specific error metrics against the reference SCS-MP3/CBS ∆ isom E (Table 1) (QZVP,p), and 6-311++G(2d,2p)) or two (cc-pVTZ) outliers present with maximum absolute deviations ranging from 13.8 to 17.8 kcal mol −1 depending on the basis set, also similar to that of the PBE0 (MAXD=9.1 kcal mol −1 ; 0 outliers), B2GP-PLYP-D (MAXD=11.5 kcal mol −1 ; 1 outlier), BMK-D (MAXD=17.1 kcal mol −1 ; 1 outlier), and PW6B95-D (MAXD=11.9 kcal mol −1 ;

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“…Despite of the superior performance of DFT methods in numerous energy assessments and molecular structure predictions, there is increasing awareness that B3LYP 22 can fail badly in estimating the energies of non-bonded interactions, hydrogen bonded systems, and larger molecules. [24][25][26][27] To overcome these disadvantages, some of the hybrid meta-GGA such as MPWB1K and MPW1B95 were developed. 28,29 These can provide more accurate assessment of weakly bound systems and better descriptions of intramolecular non-bonded interactions.…”

Section: Methodsmentioning

confidence: 99%

Molecular Dynamics Simulation and Density Functional Theory Investigation for Thiacalix[4]biscrown and its Complexes with Alkali-Metal Cations

Hong¹,

Lee²,

Ham

2010

Bulletin of the Korean Chemical Society

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The structural and energetic preferences of thiacalix [4]biscrown-5 with and without alkali metal ions (Na + , K + , Rb + , and Cs + ) have been theoretically investigated for the first time using molecular dynamic (MD) simulations and density functional theory (MPWB1K/6-31G(d)//B3LYP/6-31G(d)) methods. The formation of the metal ion complex by the host is mainly driven by the electrostatic attraction between crown-5 oxygens and a cation together with the minor contribution of the cation-π interaction between two facing phenyl rings around the cation. The computed binding energies and the atomic charge distribution analysis for the metal binding complexes indicate the selectivity toward a potassium ion. The theoretical results herein explain the experimentally observed extractability order by this host towards various alkali metal ions. The physical nature and the driving forces for cation recognition by this host are discussed in detail.

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Many Density Functional Theory Approaches Fail To Give Reliable Large Hydrocarbon Isomer Energy Differences

Cited by 313 publications

References 16 publications

Double-hybrid density functionals: merging wavefunction and density approaches to get the best of both worlds

Double-hybrid density functionals: merging wavefunction and density approaches to get the best of both worlds

Performance of the M062X density functional against the ISOL set of benchmark isomerization energies for large organic molecules

Molecular Dynamics Simulation and Density Functional Theory Investigation for Thiacalix[4]biscrown and its Complexes with Alkali-Metal Cations

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