A Systematic Failing of Current Density Functionals:  Overestimation of Two-Center Three-Electron Bonding Energies

Braı̈da, Benoı̂t; Hiberty, Philippe C.; Savin, Andreas

doi:10.1021/jp982441z

Cited by 242 publications

(228 citation statements)

References 34 publications

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“…An examination of the DFT methods led to the conclusion that similar results were obtained both with BH&HLYP as with the CCSD(T) approach [18][19][20]. We used also the PBE0 model, based on the Perdew-Burke-Erzenrhof exchange-correlation functional [21,22] and we showed that the results were totally in agreement with those of BH&HLYP.…”

Section: Structure Of the Methionine Free Radicalssupporting

confidence: 64%

Methionine one-electron oxidation: Coherent contributions from radiolysis, IRMPD spectroscopy, DFT calculations and electrochemistry

Scuderi

Bergès

Oliveira

et al. 2016

Radiation Physics and Chemistry

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Methionine is an essential amino acid, unfortunately prone to oxidation. The mechanism of its oxidation by • OH radicals has been studied for more than 40 years and still remains misunderstood. We have reinvestigated the oxidation of this residue in model peptides, aiming at i) improving the identification of free radicals by the use of more modern quantum chemistry methods; ii) reinvestigating the one-electron reduction potentials as a function of the position in the sequence; iii) identifying the final compounds, which were still unknown; iv) reinvestigating the intramolecular electron transfer (IET) involving this residue.

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Section: Structure Of the Methionine Free Radicalssupporting

confidence: 64%

Methionine one-electron oxidation: Coherent contributions from radiolysis, IRMPD spectroscopy, DFT calculations and electrochemistry

Scuderi

Bergès

Oliveira

et al. 2016

Radiation Physics and Chemistry

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“…Second, on the basis of B3LYP/6-311ϩG* optimized structures, single point calculations have been carried out at the BHLYP/6-311ϩG* ͑with 50% exchange mixing͒ level, because it is comparable to post-Hartree-Fock and is better than the former. 12,27,28 In comparison to the binding energy of 233.2 kcal/mol obtained at the MP2/6-311ϩG(2d,2p)//MP2/6-31G* level in Ref. 15, the binding energy for ͑ϩ2͒-OO at the BHLYP/6-311ϩG*//B3LYP/6-311ϩG* level is 234.4 kcal/ mol ͑see Table VIII͒, only slightly higher than the former.…”

Section: Binding Energymentioning

confidence: 77%

Glycine-Zn+/Zn2+ and their hydrates: On the number of water molecules necessary to stabilize the switterionic glycine-Zn+/Zn2+ over the nonzwitterionic ones

Ai¹,

Han

2003

The Journal of Chemical Physics

101

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Several interaction modes of glycine with one Zn ϩ or Zn 2ϩ and further with one and even two H 2 O molecules in the gas phase are studied at the hybrid three-parameter B3LYP and Hartree-Fock level, respectively. On the basis of these optimized geometries, single point calculations are performed using different theoretical methods and larger basis sets. The calculated results imply that the most stable glycine-Zn ϩ isomer is a five-membered ring with Zn ϩ bound to both amino nitrogen and carbonyl oxygen ͑NO͒ of glycine, and the next most stable glycine-Zn ϩ species is a four-membered ring with Zn ϩ coordinated at both oxygen ends ͑OO͒ of the zwitterionic glycine. The binding energy of the most stable glycine-Zn ϩ is 68.5 kcal/mol calibrated at the BHLYP/6-311ϩG*//6-311ϩG* level. On the contrary with glycine-Zn ϩ isomers, the most stable glycine-Zn 2ϩ species holds the similar coordination mode to that of next most stable glycine-Zn 2ϩ complex, while the next most stable glycine-Zn 2ϩ exhibits the similar coordination mode to that of the most stable glycine-Zn ϩ . The binding strength of these glycine-Zn 2ϩ isomers are all far more than those of their corresponding counterparts of glycine-Zn ϩ isomers, such as the binding energy of the most stable glycine-Zn 2ϩ being 234.4 kcal/mol, showing stronger electrostatic interaction. The reoptimization for the two most stable modes with the different valent states ͑ϩ1,ϩ2͒ to combine a H 2 O molecule at their each end of Zn ion show that the relative energy ordering does not change, and also resembles their no-H 2 O-combined counterparts. However, an interesting and important observation has been first obtained that single hydration effect can strikingly strengthen the stability of the monovalent OO form though it is still higher by 0.1 kcal/mol in energy than the NO counterpart. Hydration effect of double waters can reverse their relative stability due to the strong hydrogen bond effect in the OO form. Different from the case of the two monovalent hydrated complexes, calculated results for the divalent zinc ion chelated complexes show that with or without single hydration hardly change the value of their relative energy, and hydration strength and glycine deformation difference induced with or without hydration in the two different modes display surprising similarity. So we predict that the further hydration basically do not yield any effect on the relative stability. The prediction for the hydration effect on the glycine-Zn ϩ /Zn 2ϩ system would be also suitable for its analogs, such as glycine-Cu ϩ /Cu 2ϩ and glycine-Ni ϩ /Ni 2ϩ systems, and even suitable for other similar transition metal ion-chelated glycine systems.

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“…[68]. As shown in Figure 3, due to the accurate treatment of medium-range electron correlation effects [68], the predicted reaction Owing to the severe SIEs associated with semilocal functionals, spurious fractional charge dissociation can occur for symmetric charged radicals [70][71][72][73][74]. To investigate how the SCAN-based hybrid and double-hybrid functionals improve upon the SIE problems, spinunrestricted calculations are performed for the dissociation energy curves of He + 2 and Ar + 2 .…”

Section: Resultsmentioning

confidence: 99%

SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters

Hui

Chai

2016

The Journal of Chemical Physics

150

147

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By incorporating the nonempirical SCAN semilocal density functional [Sun, Ruzsinszky, and Perdew, Phys. Rev. Lett. 115, 036402 (2015)] in the underlying expression of four existing hybrid and double-hybrid models, we propose one hybrid (SCAN0) and three double-hybrid (SCAN0-DH, SCAN-QIDH, and SCAN0-2) density functionals, which are free from any fitted parameters. The SCAN-based double-hybrid functionals consistently outperform their parent SCAN semilocal functional for self-interaction problems and noncovalent interactions. In particular, SCAN0-2, which includes about 79% of Hartree-Fock exchange and 50% of second-order Møller-Plesset correlation, is shown to be reliably accurate for a very diverse range of applications, such as thermochemistry, kinetics, noncovalent interactions, and self-interaction problems.

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A Systematic Failing of Current Density Functionals: Overestimation of Two-Center Three-Electron Bonding Energies

Cited by 242 publications

References 34 publications

Methionine one-electron oxidation: Coherent contributions from radiolysis, IRMPD spectroscopy, DFT calculations and electrochemistry

Methionine one-electron oxidation: Coherent contributions from radiolysis, IRMPD spectroscopy, DFT calculations and electrochemistry

Glycine-Zn+/Zn2+ and their hydrates: On the number of water molecules necessary to stabilize the switterionic glycine-Zn+/Zn2+ over the nonzwitterionic ones

SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters

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