Performances of recently-proposed functionals for describing disulfide radical anions and similar systems

Dumont, Élise; Laurent, Adèle D.; Assfeld, Xavier; Jacquemin, Denis

doi:10.1016/j.cplett.2010.11.062

Cited by 20 publications

(32 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This group studied the performances of various DFT functional for the investigation on disulphide radical anion and similar systems along with high-level ab initio methods like MP2 and MP4. They found that the LC-BLYP functional along with few other range-separated hybrid functionals satisfy both the geometric and energetic criteria and also established the reliability and accuracy of these functionals for studying 2c-3e bond [17]. The reliability of the method will be further discussed and the results compared with available experimental data (binding energies, distances in the heteroaromatic ring and vibrational frequencies) in the next paragraphs.…”

Section: Computational Methodologymentioning

confidence: 93%

See 1 more Smart Citation

Theoretical study of the interaction between pyridine derivatives and atomic chlorine. Substituent effect and nature of the bonding

2015

View full text Add to dashboard Cite

The interaction of pyridine derivatives (H, ) with atomic chlorine is investigated theoretically by the density functional theory (DFT)-based LC-BLYP/aug-cc-pVDZ method. Pyridines and Cl • are held together by a (2c-3e) bond and the intermolecular distances range from 2.313 to 2.343Å. The existence of a N. . .Cl bond is confirmed by the atom-in-molecule analysis of the systems. The binding energies of the adducts, ranging from −42.08 to −53.96 kJ mol −1 , are linearly correlated to the proton affinity of the pyridines. The charge transfer from pyridine to Cl • varies between 0.222 and 0.277 e. The spin density analysis shows that the strongest complex has the highest (2c-3e) character. The CH bonds are contracted and the ν(CH) vibrations are blueshifted owing to the decrease in σ * (CH) occupation. This decrease results not only from the classical anomeric effect but also from the σ (CC) and σ (CN) → σ * (CH) delocalisation in the heteroaromatic ring.

show abstract

Section: Computational Methodologymentioning

confidence: 93%

“…Dumont et al in their recent work showed the reliability of LC-BLYP functional for studying the interaction formed by 2c-3e bond [17]. This group studied the performances of various DFT functional for the investigation on disulphide radical anion and similar systems along with high-level ab initio methods like MP2 and MP4.…”

Section: Computational Methodologymentioning

confidence: 97%

Theoretical study of the interaction between pyridine derivatives and atomic chlorine. Substituent effect and nature of the bonding

2015

View full text Add to dashboard Cite

show abstract

“…The discrepancy between the energies is a measure of the difference between the PBE and ED densities; recall the derivation of Eq. (20). The mean absolute percentage difference between PBE and ED exchange-correlation energies is 0.8%.…”

Section: Analysis and Performancementioning

confidence: 96%

“…(13) using the GGA density of the N-electron system, for that calculated value of k, with m = 1, and use this quantity in the calculation of α using Eq. (20). Finally, we perform a self-consistent calculation on the N-electron system using the functional in Eqs.…”

Section: mentioning

confidence: 99%

“…These conditions have been widely and successfully used [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] to "tune" orbital-dependent, global and range-separated hybrid functionals within the GKS formalism. The a) Electronic mail: d.j.tozer@durham.ac.uk HOMO and LUMO energies vary systematically with the parameter defining the amount of (long-range) exact orbital exchange and so this parameter is varied on a system-bysystem basis in order to approximately satisfy one or both of the conditions.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

System-dependent exchange–correlation functional with exact asymptotic potential and εHOMO ≈ − I

Gledhill

Tozer

2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

Density scaling considerations are used to derive an exchange–correlation explicit density functional that is appropriate for the electron deficient side of the integer and which recovers the exact r → ∞ asymptotic behaviour of the exchange–correlation potential. The functional has an unconventional mathematical form with parameters that are system-dependent; the parameters for an N-electron system are determined in advance from generalised gradient approximation (GGA) calculations on the N- and (N − 1)-electron systems. Compared to GGA results, the functional yields similar exchange–correlation energies, but HOMO energies that are an order of magnitude closer to the negative of the vertical ionisation potential; for anions, the HOMO energies are negative, as required. Rydberg excitation energies are also notably improved and the exchange–correlation potential is visibly lowered towards the near-exact potential. Further development is required to improve valence excitations, static isotropic polarisabilities, and the shape of the potential in non-asymptotic regions. The functional is fundamentally different to conventional approximations.

show abstract

Unraveling redox pathways of the disulfide bond in dimethyl disulfide: Ab initio modeling

Ould Mohamed,

Abtouche,

Ghoualem

et al. 2024

J Mol Model

View full text Add to dashboard Cite

Performances of recently-proposed functionals for describing disulfide radical anions and similar systems

Cited by 20 publications

References 46 publications

Theoretical study of the interaction between pyridine derivatives and atomic chlorine. Substituent effect and nature of the bonding

Theoretical study of the interaction between pyridine derivatives and atomic chlorine. Substituent effect and nature of the bonding

System-dependent exchange–correlation functional with exact asymptotic potential and εHOMO ≈ − I

Unraveling redox pathways of the disulfide bond in dimethyl disulfide: Ab initio modeling

Contact Info

Product

Resources

About