Tetrasulfur tetranitride and its selenium analogs: ab initio and DFT calculations

Chung, Gyusung; Lee, Duckhwan

doi:10.1016/s0166-1280(01)00769-2

Cited by 9 publications

(10 citation statements)

References 17 publications

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“…Compound 1 has a highly symmetric cage-structure ( D 2 d ) in both the crystalline state and the gas phase . This structure was well reproduced in recent density functional theory (DFT) calculations .…”

Section: Introductionsupporting

confidence: 61%

Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study

et al. 2012

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The photochemistry of tetrasulfur tetranitride (1) was studied in hexane solution by the laser flash photolysis technique (LFP). The experimental findings were interpreted using the results of previous matrix isolation studies (Pritchina, E.A.; Gritsan, N.P.; Bally, T.; Zibarev, A.V. Inorg. Chem. 2009, 48, 4075) and high-level quantum chemical calculations. LFP produces two primary intermediates, one of which is the boat-shaped 8-membered cyclic compound (2) and the other is the 6-membered S(3)N(3) cyclic compound carrying an exocyclic (S)-N═S group (3). The primary products 2 and 3 absorb a second photon and undergo transformation to the 6-membered S(3)N(3) cycle carrying an exocyclic (N)-S≡N group (4), which is very unstable and converts back to intermediate 3. The quantum yield of the primary product formation is close to unity even though the quantum yield of photodegradation of 1 is low (~0.01). Thus, 1 is a photochromic compound undergoing in solution the thermally reversible photochemical isomerization. The mechanism of the photochromic process was established, and the rate constants of the elementary reactions were measured.

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Section: Introductionsupporting

confidence: 61%

Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study

et al. 2012

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“…The calculated 77 Se chemical shifts of Se 2 S 2 N 4 have slightly larger errors, and all methods uniformly predict chemical shifts that are around 200 ppm too small. This is expected since these cage structures exhibit weak transannular E···E bonding interactions which are known to be difficult to model accurately …”

Section: Resultsmentioning

confidence: 99%

Electronic Structures and Molecular Properties of Chalcogen Nitrides Se₂N₂ and SeSN₂

et al. 2005

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The electronic structures and molecular properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 have been studied using various ab initio and density functional methods. All molecules share a qualitatively similar electronic structure and can be primarily described as 2π-electron aromatics having minor singlet diradical character of 68% that can be attributed solely to the nitrogen atoms. This

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“…19 As discussed in the introduction, the HF method underestimates the E⋯E contacts in E4N4 and particularly in E8 2+ , whereas MP2 predicts virtually no interaction between the two chalcogen centers in either system. 25,29,30 The data in Figure 2 shows that the established trends persist also when using these methods together with modern DFT is formally a single determinant method and hence it is natural to discuss the results obtained with different density functionals in the current context. The data in Figure 2 shows a clear trend towards shorter E⋯E contacts when the amount of exact exchange in the functional is increased.…”

Section: Resultsmentioning

confidence: 98%

“…29 Moreover, any attempt to include electron correlation effects in either case by means of second order perturbation theory (MP2) leads to significant overestimation of the E⋯E interaction. 25,29 Even density functional theory (DFT) has difficulties in providing a consistent picture of bonding in these systems and the results are highly dependent of the chosen functional and the amount of exact exchange employed. For example, the B3LYP hybrid functional predicts the cross-ring S⋯S distances in dithiatetrazocines rather accurately, 21 but for no obvious reasons it overestimates those in S4N4 and E8 2+ .…”

Section: Introductionmentioning

confidence: 99%

“…For example, the B3LYP hybrid functional predicts the cross-ring S⋯S distances in dithiatetrazocines rather accurately, 21 but for no obvious reasons it overestimates those in S4N4 and E8 2+ . 25,40 On the other hand, the non-hybrid version of the same functional, namely BLYP, has considerable difficulties in reproducing the transannular interactions in E8 2+ , 29 whereas the MPW91PW91 functional is known to provide highly accurate bond lengths even when combined with very small basis sets. 19 Based on the current theoretical data for 14, it is safe to conclude that a solid physical explanation of their weak cross-ring bonds is still lacking.…”

Section: Introductionmentioning

confidence: 99%

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The Nature of Transannular Interactions in E₄N₄ and E₈²⁺ (E = S, Se)

Moilanen

Karttunen

Tuononen

et al. 2012

J. Chem. Theory Comput.

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The electronic structures of tetrachalcogen tetranitrides, E4N4, and octachalcogen dications, E8 2+ , and the nature of their transannular E⋯E interactions (E = S, Se) was studied with high-level theoretical methods. The results reveal that the singlet ground states of both systems have a surprisingly large correlation contribution which functions to weaken and therefore lengthen the cross-ring EE bond. The observed correlation effects are primarily static in E4N4, whereas in E8 2+ the dynamic part largely governs the total correlation contribution. The presented description of bonding is the first that gives an all-inclusive picture of the origin of cross-ring interactions in E4N4 and E8 2+ ; not only does it succeed in reproducing all experimental structures but it also offers a solid explanation for the sporadic performance of different computational methods that has been reported in previous studies.Furthermore, the theoretical data demonstrate that E⋯E bonds in E4N4 and E8 2+ are unique and fundamentally different from, for example, dispersion that plays a major role in weak intermolecular chalcogen⋯chalcogen contacts.3

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Tetrasulfur tetranitride and its selenium analogs: ab initio and DFT calculations

Cited by 9 publications

References 17 publications

Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study

Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study

Electronic Structures and Molecular Properties of Chalcogen Nitrides Se₂N₂ and SeSN₂

The Nature of Transannular Interactions in E₄N₄ and E₈²⁺ (E = S, Se)

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Tetrasulfur tetranitride and its selenium analogs: ab initio and DFT calculations

Cited by 9 publications

References 17 publications

Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study

Photochemistry of Tetrasulfur Tetranitride: Laser Flash Photolysis and Quantum Chemical Study

Electronic Structures and Molecular Properties of Chalcogen Nitrides Se2N2 and SeSN2

The Nature of Transannular Interactions in E4N4 and E82+ (E = S, Se)

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Electronic Structures and Molecular Properties of Chalcogen Nitrides Se₂N₂ and SeSN₂

The Nature of Transannular Interactions in E₄N₄ and E₈²⁺ (E = S, Se)