Organic Superhalogens

Giri, Santanab; Child, Brandon Z.; Jena, P.

doi:10.1002/cphc.201402472

Cited by 32 publications

(67 citation statements)

References 33 publications

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“…Taking [Mg2F5] -1 (a2 in Fig. Similar situation takes place 20 in the composite structures with Cl atom too as shown in Fig. This double-bridged superhalogen [Mg2F5] -1 removes F4 atom to form the type II substituent and it removes F2 or F3 atom to form the type III substituent.…”

Section: Theoretical Methods and Computational Detailsmentioning

confidence: 66%

“…Compared with CCSD(T), OVGF fails for the composite 20 structures with Cl atom and thus its reliability is questionable. Although there are deviations from CCSD(T) results in the aspect of absolute value of VDE, the relative order of VDEs with MP2 is generally consistent with CCSD(T).…”

Section: Discussionmentioning

confidence: 99%

“…The equilibrium geometries of the species studied here were 20 optimized at MP2 39 level with the 6-311+G* basis set. 40,41 The obtained structures are confirmed to be local minima by the nonexistence of imaginary frequency.…”

Section: Theoretical Methods and Computational Detailsmentioning

confidence: 99%

“…[10][11][12] Albeit the F, Cl, and CN species are considered relatively effective oxidizing agents (due to their large electron affinities spanning the 3.40~3.90 eV range) [13][14][15] the resulting C2H3X, C2H5X, and C6H5X molecules (X = F, Cl, CN) do not bind an excess electron to form 45 electronically stable anions. That is to say, the organic molecules, of which the anionic forms are unstable, [10][11][12][20][21][22] will produce stable anions after introducing superhalogen- 55 like substituent. These composite structures, 19 generated 50 from the combination of organic molecules of small or even negative VDE with superhalogens, possess VDE values apparently higher than their organic parents.…”

Section: Introductionmentioning

confidence: 99%

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Is the regulation of the electronic properties of organic molecules by polynuclear superhalogens more effective than that by mononuclear superhalogens? A high-level ab initio case study

Bai

et al. 2015

Phys. Chem. Chem. Phys.

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The regulation of the electronic properties of organic molecules induced by polynuclear superhalogens is theoretically explored here for sixteen composite structures. It is clearly indicated by the higher vertical electron detachment energy (VDE) that polynuclear superhalogens are more effective in regulating the electronic properties than mononuclear structures. However, this enhanced regulation is not only determined by superhalogens themselves but also related to the distribution of the extra electron of the final composites. The composites, in which the extra electron is mainly aggregated into the superhalogen moiety, will possess higher VDE values, as reported in the case of C1', 7.12 eV at the CCSD(T) level. This is probably due to the fact that, compared with organic molecules, superhalogens possess stronger attraction towards the extra electron and thus should lead to lower energies of the extra electrons and to higher VDE values eventually. Compared with CCSD(T), the Outer Valence Green's Function (OVGF) method fails completely for composite structures containing Cl atoms, while MP2 results are generally consistent in terms of the relative order of VDEs. Actually if the extra electron distribution of the systems could be approximated by the HOMO, the results at the OVGF level will be consistent with the CCSD(T) results. Conversely, the difference in VDEs between OVGF and CCSD(T) is significantly large. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to various fragmentation channels were also investigated for all the composite structures.

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Section: Theoretical Methods and Computational Detailsmentioning

confidence: 66%

Section: Discussionmentioning

confidence: 99%

Section: Theoretical Methods and Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Is the regulation of the electronic properties of organic molecules by polynuclear superhalogens more effective than that by mononuclear superhalogens? A high-level ab initio case study

Bai

et al. 2015

Phys. Chem. Chem. Phys.

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“…Recently,s chemes making use of electron-counting rules have been developed [20,21] to systematically increase the EAs of organic molecules even further, making them behave like superhalogens. For example, the EA of C 5 H 5 can be increased to 5.59 eV by replacing Hw ith CN.…”

Section: Introductionmentioning

confidence: 99%

From Halogen to Superhalogen Behavior of Organic Molecules Created by Functionalizing Benzene

et al. 2015

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Benzene, the classic organic molecule obeying Hückel's rule of aromaticity, has negative electron affinity (EA), namely -1.15 eV. By using density functional theory with hybrid functional for exchange and correlation potential, we show that a series of organic molecules created by changing either the benzene core or the ligands, or both, result in species with EAs that range from 2.15 to 5.37 eV. This shows that ligand substitution is more effective than aromaticity in increasing the EA of organic molecules. The ability to create highly electronegative organic molecules by functionalizing benzene may provide new opportunities for synthesizing organic oxidizing agents with potential new applications.

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