Quantum mechanical ab initio studies of the structures and stabilities of halogen azides XN3 (X = F, Cl, Br, I)

Otto, Michael; Lotz, Simon; Frenking, Gernot

doi:10.1021/ic00043a028

Cited by 72 publications

(42 citation statements)

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“…However, Frenking et al have shown that for halogen azides XN3 (X = halogen) the reaction energy of the dissociation reaction of XN 3 ( 1 A') yielding N2 ( 1 Σg + ) and XN ( 3 Σ -) can be calculated at the electron-correlated MP2 level of theory using effective core potentials for the heavy elements MP2/LANL1DZ+P. 39 Generally, the agreement between the theoretical and experimental data for the heat of formation calculated at the MP2 level (DZ+P basis set) is very good for HN 3 . 40 This gives credence to those calculated dissociation energies for which there are no experimental data due to the extreme lability of the compounds in question.…”

Section: Structure and Bondingmentioning

confidence: 99%

“…[42][43][44][45][46] Experimentally the structure of IN3 was determined in the solid state (X-ray) 42 as well as in the gas phase (ED, MW) [43][44] and several ab initio and DFT computations have been reported. 12b, 39,42 HN3 and halogen azides X-Nl-N2-N3 present as discrete monomeric species in the gas phase display a bent trans Cs configuration with an Nl-N2-N3 bond angle of 172 ± 3 o , and two significantly different N-N bond lengths (N1-N2 = 1.24 (2) Å, N2-N3 = 1.160 (5) Å, Fig. 1).…”

Section: Structure and Bondingmentioning

confidence: 99%

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Inorganic and Transition Metal Azides

Seok

Klapötke

2010

Bulletin of the Korean Chemical Society

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Experimental and theoretical studies show that all covalent azides possess a nonlinear azide group. They also rationalize this remarkable structural feature. We have seen that the most important non-covalent contributions in the covalently bound azides system (X-N1-N2-N3) are the π-delocalization over the entire molecule and a strong negative hyperconjugation which donates electron density from the filled σ (X-N1) orbital into the unfilled, antibonding π* (N2-N3) orbital. For transition metal azide complexes, a bent configuration and a small difference between the N-N bond lengths, generally the longer one being adjacent to the transition metal, were observed.

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Section: Structure and Bondingmentioning

confidence: 99%

Section: Structure and Bondingmentioning

confidence: 99%

Inorganic and Transition Metal Azides

Seok

Klapötke

2010

Bulletin of the Korean Chemical Society

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“…This holds, for example, for experimentally known high-energy compounds like fluoro-A C H T U N G T R E N N U N G azide, FN 3 , where the bond rupture FN 3 !FN + N 2 is calculated to be exothermic by approximately À25 kcal mol À1 . [13] It holds particularly for doubly and more highly charged cations that are often metastable, that is, they are local minima on the PES although the dissociation into singly charged fragments is exothermic. [14] A pertinent example is He 2 2 + , which was already predicted to be metastable by Pauling in 1933.…”

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confidence: 99%

Is This a Chemical Bond? A Theoretical Study of Ng₂@C₆₀(Ng=He, Ne, Ar, Kr, Xe)

Krapp

Frenking

2007

Chemistry A European J

185

196

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Quantum-chemical calculations using DFT (BP86) and ab initio methods (MP2, SCS-MP2) have been carried out for the endohedral fullerenes Ng2@C60 (Ng=He-Xe). The nature of the interactions has been analyzed with charge- and energy-partitioning methods and with the topological analysis of the electron density (Atoms-in-Molecules (AIM)). The calculations predict that the equilibrium geometries of Ng2@C60 have D3d symmetry when Ng=Ne, Ar, Kr, while the energy-minimum structure of Xe2@C60 has D5d symmetry. The precession movement of He2 in He2@C60 has practically no barrier. The Ng--Ng distances in Ng2@C60 are much shorter than in free Ng2. All compounds Ng2@C60 are thermodynamically unstable towards loss of the noble gas atoms. The heavier species Ar2@C60, Kr2@C60, and Xe2@C60 are high energy compounds which are at the BSSE corrected SCS-MP2/TZVPP level in the range 96.7-305.5 kcal mol(-1) less stable than free C60+2 Ng. The AIM method reveals that there is always an Ng--Ng bond path in Ng2@C60. There are six Ng--C bond paths in (D3d) Ar2@C60, Kr2@C60, and Xe2@C60, whereas the lighter D3d homologues He2@C60 and Ne2@C60 have only three Ng--C2 paths. The calculated charge distribution and the orbital analysis clearly show that the bonding situation in Xe2@C60 significantly differs from those of the lighter homologues. The atomic partial charge of the [Xe2] moiety is +1.06, whereas the charges of the lighter dimers [Ng2] are close to zero. The a2u HOMO of (D3d) Xe2@C60 in the 1A1g state shows a large mixing of the highest lying occupied sigma* orbital of [Xe2] and the orbitals of the C60 cage. There is only a small gap between the a2u HOMO of Xe2@C60 and the eu LUMO and the a2u LUMO+1. The calculations show that there are several triplet states which are close in energy to each other and to the 1A1g state. The bonding analysis suggests that the interacting species in Xe2@C60 are the charged species Xe2q+ and C60q-, where 1

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“…The structures and vibrational data of all these azides (X = F, CI, Br, I) have been determined experimentally and theoretically [3,4]. It has been shown by us and others that electron-correlated ab initio computations at the MP2 level [3] as well as density functional calculations at the B-LYP level of theory [4] are very suitable to predict both the geometries as well as frequencies of these species.…”

Section: Introductionmentioning

confidence: 99%

The structure of astatine azide, AtN3—A theoretical study

Klapötke

Schulz

1997

Struct Chem

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For the first time theoretical evidence for the experimentally hitherto unknown astatine azide, AtN 3, the heaviest of all halogen azides, is presented. The structure and the vibrational data of AtN3 were computed ab initio at RHF and electron-correlated MP2 levels of theory using a quasirelativistic (MWB) pseudopotential for astatine, where the basis functions for the valence s and p electrons consist of the standard double-~" basis set. For nitrogen a standard 6-31G(d) basis was used. The molecule represents a true minimum (NIMAG = 0) at all levels of theory applied and is predicted to exist in a planar trans bent Cs structure. Since hybrid functionals, which define the exchange functional as a linear combination of Hartree-Fock, local, and gradient-corrected exchange terms, are known to predict the experimental parameters best, we also computed astatine azide (

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Quantum mechanical ab initio studies of the structures and stabilities of halogen azides XN3 (X = F, Cl, Br, I)

Cited by 72 publications

References 2 publications

Inorganic and Transition Metal Azides

Inorganic and Transition Metal Azides

Is This a Chemical Bond? A Theoretical Study of Ng₂@C₆₀(Ng=He, Ne, Ar, Kr, Xe)

The structure of astatine azide, AtN3—A theoretical study

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Quantum mechanical ab initio studies of the structures and stabilities of halogen azides XN3 (X = F, Cl, Br, I)

Cited by 72 publications

References 2 publications

Inorganic and Transition Metal Azides

Inorganic and Transition Metal Azides

Is This a Chemical Bond? A Theoretical Study of Ng2@C60(Ng=He, Ne, Ar, Kr, Xe)

The structure of astatine azide, AtN3—A theoretical study

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Is This a Chemical Bond? A Theoretical Study of Ng₂@C₆₀(Ng=He, Ne, Ar, Kr, Xe)