The Theoretical Investigation of the Electron Affinity of Chemical Compounds

Gutsev, G. L.; Boldyrev, Alexander I.

doi:10.1002/9780470142851.ch3

Cited by 119 publications

(89 citation statements)

References 114 publications

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“…The high binding energy of an extra electron in a MX kþ1 À anion is due to delocalization of the extra electron over the large number of ligand atoms. Superhalogens with polyvalent ligands are described by the formula [10] MX k/mþ1 where k is the maximal formal valence of M and m is the normal valence of X that factors m, for example, ClO 4 or PO 3 . No exception to the superhalogen formula was found in studies of halogen-containing superhalogens MX 2 (M ¼ Li, Na; X ¼ Cl, Br, I), [11][12][13] MX 3 (M ¼ Be, Mg, Ca; X ¼ Cl, Br), [14][15][16] OF 3 , [17] MX 4 (M ¼ B, Al; X ¼ F, Cl, Br), [18][19][20] SiF 5 , [21] SiCl 5 , [22] GeF 5 , [23] PF 6 , [24] and PCl 6 .…”

Section: Introductionmentioning

confidence: 99%

Structure and properties of the aluminum borates Al(BO₂)_n and Al(BO₂)_n⁻, (n = 1–4)

et al. 2011

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The geometrical and electronic structures of Al(BO(2))(n) and Al(BO(2))(n)(-) (n = 1-4) clusters are computed at different levels of theory including density functional theory (DFT), hybrid DFT, double-hybrid DFT, and second-order perturbation theory. All aluminum borates are found to be quite stable toward the BO(2) and BO(2)(-) loss in the neutral and anion series, respectively. Al(BO(2))(4) belongs to the class of hyperhalogens composed of smaller superhalogens, and should possess a large adiabatic electron affinity (EA(ad)) larger than that of its superhalogen building block BO(2). Indeed, the aluminum tetraborate possesses the EA(ad) of 5.6 eV, which, however, is smaller than the EA(ad) of 7.8 eV of the AlF(4) supehalogen despite BO(2) is more electronegative than F. The EA(ad) decrease in Al(BO(2))(4) is due to the higher thermodynamic stability of Al(BO(2))(4) compared to that of AlF(4). Because of its high EA and thermodynamic stability, Al(BO(2))(4) should be capable of forming salts with electropositive counter ions. We optimized KAl(BO(2))(4) as corresponding to a unit cell of a hypothetical KAl(BO(2))(4) salt and found that specific energy and energy density of such a salt are competitive with those of trinitrotoluol (TNT).

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Section: Introductionmentioning

confidence: 99%

Structure and properties of the aluminum borates Al(BO₂)_n and Al(BO₂)_n⁻, (n = 1–4)

et al. 2011

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“…One of the most exciting developments in the field of clusters is the realization that stable atomic clusters with suitable size and composition can be designed to mimic the chemical behavior of atoms in the periodic table and, consequently, can be described as superatoms [1]. Since the 1980s, there has been increased interest and activity in experimental and theoretical investigations of two kinds of typical superatoms, namely, superhalogens [2][3][4][5][6][7][8][9][10][11][12] and superalkalies [13][14][15][16][17] initially introduced in chemistry by Gutsev and Boldyrev. Superhalogens with high electron affinities (EAs) are of a great importance in chemistry because they can be used for the oxidation of counterpart systems with relatively high ionization potentials.…”

Section: Introductionmentioning

confidence: 99%

Structural properties and nonlinear optical responses of superatom compounds BF₄‐M (M = Li, FLi₂, OLi₃, NLi₄)

Yang

Liu

et al. 2011

Int J of Quantum Chemistry

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A new type of superhalogen-(super)alkali compound, BF 4 -M (M ¼ Li, FLi 2 , OLi 3 , NLi 4 ), is theoretically characterized at the MP2/6-311þG(3df) level. The interaction between superhalogen BF 4 and different shaped (super)alkali M is found to be strong and ionic in nature. Bond energies of these BF 4 -M species are in the range of 200.0-226.7 kcal/mol at the CCSD(T)/6-311þG(3df) level, which are much larger than the traditional ionic bond energy of 130.1 kcal/mol of FLi. In addition, different from the alkali halides, the BF 4 -M compounds prefer to dissociate into ions rather than neutral fragments. The energetic properties of BF 4 -M are found to be closely related to the size of the M subunit. The different effects of superalkali and superhalogen subunits on the nonlinear optical (NLO) properties of such superatom compounds are also revealed.

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“…Gutsev and Boldyrev [1] proposed a simple formula for superhalogens MX (n?1)/m , where, n is the maximal formal valence of the central atom (M), and m is the normal valence of electronegative atom (X). Pioneering work of Gutsev and Boldyrev [2] on theoretical investigation of electron affinities of chemical compounds is also a milestone for search of new superhalogen compounds. As a part of their ongoing research on superhalogen, Gutsev and Boldyrev [3] also calculated the electronic structure of the 3d and 4d metal hexafluoride anions.…”

Section: Introductionmentioning

confidence: 99%

First principle study of CrF n (n = 1–7) nano clusters: An investigation of superhalogen properties

Siddiqui

2011

Struct Chem

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Quantum chemical calculations using gradient corrected density functional theory at B3LYP level reveals the unusual properties of a chromium (Cr) atom interacting with fluorine (F) atoms. Up to seven F atoms are bound to a single Cr atom, which results in increase of electron affinities as successive fluorine atoms are attached, reaching a peak value of 7.14 eV for CrF 6 . The large HOMO-LUMO energy gap, both in neutral and anionic form, further provide evidence of their stability. These unusual properties brought about by involvement of inner shell 3d-electrons, which not only allow CrF n (n = 1-7) clusters to belong to the class of superhalogens but also show that its valence can exceed the nominal value of 2.

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The Theoretical Investigation of the Electron Affinity of Chemical Compounds

Cited by 119 publications

References 114 publications

Structure and properties of the aluminum borates Al(BO₂)_n and Al(BO₂)_n⁻, (n = 1–4)

Structure and properties of the aluminum borates Al(BO₂)_n and Al(BO₂)_n⁻, (n = 1–4)

Structural properties and nonlinear optical responses of superatom compounds BF₄‐M (M = Li, FLi₂, OLi₃, NLi₄)

First principle study of CrF n (n = 1–7) nano clusters: An investigation of superhalogen properties

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The Theoretical Investigation of the Electron Affinity of Chemical Compounds

Cited by 119 publications

References 114 publications

Structure and properties of the aluminum borates Al(BO2)n and Al(BO2)n−, (n = 1–4)

Structure and properties of the aluminum borates Al(BO2)n and Al(BO2)n−, (n = 1–4)

Structural properties and nonlinear optical responses of superatom compounds BF4‐M (M = Li, FLi2, OLi3, NLi4)

First principle study of CrF n (n = 1–7) nano clusters: An investigation of superhalogen properties

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Structure and properties of the aluminum borates Al(BO₂)_n and Al(BO₂)_n⁻, (n = 1–4)

Structure and properties of the aluminum borates Al(BO₂)_n and Al(BO₂)_n⁻, (n = 1–4)

Structural properties and nonlinear optical responses of superatom compounds BF₄‐M (M = Li, FLi₂, OLi₃, NLi₄)