The electronic structure of chalcogen hexahalogenides

Gutsev, G. L.; Klyagina, A. P.

doi:10.1016/0301-0104(83)85023-x

Cited by 23 publications

(5 citation statements)

References 39 publications

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“…As in the case of SCl 5 and SCl 4 , SCl 6 is metastable with respect to the loss of Cl 2 ; as reported in Table , SCl 6 is less stable than SCl 4 + Cl 2 by 23.2 kcal/mol at the RCCSD(T)/AVQZ level of theory. Previous theoretical studies have been carried out for SCl 6 , , including a DFT calculation of the equilibrium structure and vibrational frequencies . These DFT calculations are in good agreement with our RCCSD(T)/AVQZ minimum and B3LYP/AVTZ frequencies.…”

Section: Resultssupporting

confidence: 85%

Bonding in SCl_n (n = 1−6): A Quantum Chemical Study

Leiding

Dunning

2011

J. Phys. Chem. A

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Following a previous study of bonding and isomerism in the SF(n) and singly chloro-substituted SF(n-1)Cl (n = 1-6) series, we describe bonding in the ground and low-lying excited states of the completely substituted series, SCl(n) (n = 1-6). All structures were characterized at least at the RCCSD(T)/aug-cc-pV(Q+d)Z level of theory. Both differences and similarities were observed between SCl(n) and our previous results on SF(n-1)Cl and SF(n). Several minimum structures that exist in SF(n) and SF(n-1)Cl are absent in SCl(n). For example, the optimized structure of SCl(2)((3)A(2)) is a transition state in C(s) symmetry, whereas the analogous states are minima in SF(n) and SF(n-1)Cl. Second, we found a continuation of a trend discovered in the SF(n-1)Cl series, where Cl substitution has a destabilizing effect that weakens bonds with respect to SF(n). This effect is much stronger in the SCl(n) series than it is in the SF(n-1)Cl series, which is why SCl(2) is the most stable observed species in the family and why SCl(4), SCl(5), and SCl(6) are unstable (SCl(n-2) + Cl(2) additions are endothermic for n = 4-6).

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Section: Resultssupporting

confidence: 85%

Bonding in SCl_n (n = 1−6): A Quantum Chemical Study

Leiding

Dunning

2011

J. Phys. Chem. A

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“…Gutsev and Boldyrev termed this class of clusters "superhalogens". 56,57 Superhalogens have general formula MX (n+1)/m , where M is a main group or transition metal, X is a halogen atom, n is the maximal formal valence of the central atom M, and m is the normal valence of the electronegative atom X. 56,57 Similar to valence isoelectronic BO 2 and AlO 2 , results show that GaO 2 can be classified as a superhalogen.…”

Section: Methodsmentioning

confidence: 99%

“…56,57 Superhalogens have general formula MX (n+1)/m , where M is a main group or transition metal, X is a halogen atom, n is the maximal formal valence of the central atom M, and m is the normal valence of the electronegative atom X. 56,57 Similar to valence isoelectronic BO 2 and AlO 2 , results show that GaO 2 can be classified as a superhalogen. Akin to (BO 2 ) 2 and (AlO 2 ) 2 , 35 the electron affinity of Ga 2 O 4 exceeds that of chlorine atom at the B3LYP level of theory and, therefore, it can be considered as a superhalogen.…”

Section: Methodsmentioning

confidence: 99%

Density Functional Theory and ab Initio Studies of the Structure and Energetics of Digallium Tetraoxide, Ga₂O₄, in the Gas Phase

2012

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A systematic investigation on the neutral and anionic digallium tetraoxide, Ga(2)O(4) has been carried out by using density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2), and the coupled cluster approach with single and double substitutions and a perturbative treatment of the triple excitations [CCSD(T)]. The geometry of neutral Ga(2)O(4) has been proposed earlier, from an experimental study, to adopt a D(2d) symmetry (J. Phys. Chem. 1979, 83, 656). However, the current research reveals that, out of the several isomers considered for neutral and anionic digallium tetraoxide, the (3)B(1u) and (2)B(3g) of the planar D(2h) geometry (7a-D(2h)) are the lowest-energy states for Ga(2)O(4) and Ga(2)O(4)(-). Our computations rule out the D(2d) geometry (3-D(2d)) as a viable contender for neutral Ga(2)O(4). The (3)B(2) (3-D(2d)) state is located above the (3)B(1u) (7-D(2h)) state by at least 4.26 eV. The energies of the low lying states, geometrical parameters, and energetic features (VEDE, AEDE, and AEA) are reported. The AEA of Ga(2)O(4) is calculated to be 3.94 eV (B3LYP), 3.24 eV (MP2), 3.42 eV [CCSD(T)//B3LYP], and 3.38 eV [CCSD(T)//MP2], respectively. In addition, the dissociation energy, D(e), for the process Ga(2)O(4) ((3)B(1u)) → 2GaO(2) ((2)A(2)) is 3.59 eV (B3LYP), 5.08 eV (MP2), 4.82 eV [CCSD(T)//B3LYP], and 4.80 eV [CCSD(T)//MP2]. The results obtained in this work are critically analyzed, discussed, and compared with those of the analogous metal oxides.

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“…The properties, especially the vibrational spectra, of TeF 6 have received significant attention. − The structure of TeF 6 has been obtained from a temperature dependent electron diffraction study and in the solid state by X-ray diffraction . TeF 6 has been studied computationally at the Hartree–Fock (HF), MP2 (second order Møller–Plesset perturbation theory), and density functional theory (DFT) (B88LYP, B3LYP, B88P86, and B3P86) levels. , Numerous papers have been published dealing with its electron affinity, force fields, , low energy electron attachment, potential function, first dissociative ionization energy, ionization potential, and F – affinity . The mass spectrum of TeF 6 was recently reported together with calculations on the ions at the B3LYP level with a large basis set …”

Section: Introductionmentioning

confidence: 99%

“…15 TeF 6 has been studied computationally at the Hartree−Fock (HF), MP2 (second order Møller−Plesset perturbation theory), and density functional theory (DFT) (B88LYP, B3LYP, B88P86, and B3P86) levels. 16,17 Numerous papers have been published dealing with its electron affinity, 18 force fields, 19,20 low energy electron attachment, 21 potential function, 22 first dissociative ionization energy, 23 ionization potential, 24 and F − affinity. 25 The mass spectrum of TeF 6 was recently reported together with calculations on the ions at the B3LYP level with a large basis set.…”

Section: ■ Introductionmentioning

confidence: 99%

Electronic Structure Predictions of the Energetic Properties of Tellurium Fluorides

2019

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The heats of formation, bond dissociation energies (BDEs), fluoride affinities (FA), fluorocation affinities (FCA), electron affinities (EA), and ionization energies (IP) of TeF n (n = 1−6) have been predicted using the Feller−Peterson−Dixon (FPD) approach. To benchmark the approach, the bond dissociation energies of Te 2 and TeO, the heats of formation of Te 2 , TeH 2 , TeO, and TeO 2 , and the electron affinity for TeO and TeO 2 were calculated as there are experimental thermodynamic data available for these tellurium compounds, which allow confirmation of the heat of formation of Te gas as ΔH f,0K (Te) = 50.7 ± 0.6 kcal/mol. Spin−orbit corrections are required for good results and cannot be ignored. A comparison among fluoride affinities, fluorocation affinities, electron affinities, and ionization energies of TeF n and SeF n is reported.

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The electronic structure of chalcogen hexahalogenides

Cited by 23 publications

References 39 publications

Bonding in SCl_n (n = 1−6): A Quantum Chemical Study

Bonding in SCl_n (n = 1−6): A Quantum Chemical Study

Density Functional Theory and ab Initio Studies of the Structure and Energetics of Digallium Tetraoxide, Ga₂O₄, in the Gas Phase

Electronic Structure Predictions of the Energetic Properties of Tellurium Fluorides

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The electronic structure of chalcogen hexahalogenides

Cited by 23 publications

References 39 publications

Bonding in SCln (n = 1−6): A Quantum Chemical Study

Bonding in SCln (n = 1−6): A Quantum Chemical Study

Density Functional Theory and ab Initio Studies of the Structure and Energetics of Digallium Tetraoxide, Ga2O4, in the Gas Phase

Electronic Structure Predictions of the Energetic Properties of Tellurium Fluorides

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Bonding in SCl_n (n = 1−6): A Quantum Chemical Study

Bonding in SCl_n (n = 1−6): A Quantum Chemical Study

Density Functional Theory and ab Initio Studies of the Structure and Energetics of Digallium Tetraoxide, Ga₂O₄, in the Gas Phase