Comparative study of Møller–Plesset perturbation theory and configuration interaction theory for the structure of the N<sub>4</sub><sup>+</sup> cation

Kemister, G.; Peel, J. Barrie

doi:10.1002/oms.1210280408

Cited by 11 publications

(6 citation statements)

References 12 publications

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“…In both cases, the resulting SOMO (b 2 or b 2u ) simply arises from a destabilizing interaction between both π u orbitals of both monomers. Nevertheless, the calculated energy differences of 3.71 eV (358 kJ/mol) between I1 •+ and I3 •+ and 4.25 eV (410 kJ/mol) between I1 •+ and I4 •+ do not match at all with the PES value of just 1.2 eV 13a (see also ref ). It is tempting to suggest that this second band was simply due to the 2 Π state of N 2 + cation which corresponds to a second ionization energy of 16.66 eV of N 2 and a 2 Π ← 2 Σ excitation energy of 1.14 eV of the N 2 + cation.…”

Section: Resultsmentioning

confidence: 93%

“…22b In this context, much effort has been devoted to search for a way of making a bound tetranitrogen N 4 molecule, the missing but perhaps a key member of the N n family. The abundant literature 23 points out that both the ionized N 4 •+ (refs [24][25][26][27][28][29][30][31][32] and neutral N 4 (refs 33-61) forms are the subject of intense theoretical and computational scrutiny. A recent experimental paper 62 reported on the experimental detection of N 4 , but its structural identity is not established yet.…”

Section: Introductionmentioning

confidence: 99%

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Azido-Nitrene Is Probably the N₄ Molecule Observed in Mass Spectrometric Experiments

et al. 2003

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Ab initio calculations determining structures and stabilities of the tetranitrogen N 4 •+ /N 4 system and mass spectrometric experiments were carried out in an attempt to understand the processes occurring in a recent neutralization-reionization mass spectrometric (NRMS) experiment starting from a linear N 4 •+ radical cation (Cacace et al. Science, 2002, 295, 480). Calculations were performed using RCCSD(T) and MRCISD+Q methods with the 6-311+G(3df) basis set. The most stable bound tetranitrogen molecule is an azidonitrene (N 3 -N) featuring a triplet 3 A′′ ground state and being 56 kJ/mol below the singlet tetrahedral T d isomer. The singlet azidonitrene has an open-shell 1 A′′ state and the corresponding singlet-triplet energy gap amounts to 69 kJ/mol. In both states, fragmentation giving two N 2 moieties needs to overcome a barrier height of about 55 kJ/mol. A remarkable difference between N 4 isomers is that ionization of triplet azidonitrene leads to the linear 2 Σ ground-state radical cation, whereas removal of an electron from singlet tetrahedrane (N 4 , T d ) gives rise to a cyclic three-membered ring belonging to a Π-type excited state. The standard heats of formation are evaluated as follows: ∆H°f (triplet azidonitrene) ) 714 ( 20 kJ/mol, ∆H°f (singlet azidonitrene) ) 783 ( 20 kJ/mol, ∆H°f (N 4 , T d ) ) 770 ( 20 kJ/mol, and ∆H°f (N 4 •+ ) ) 1398 ( 20 kJ/mol. The adiabatic ionization energies are estimated as IE a (triplet azidonitrene) ) 7.3 ( 0.3 eV and IE a (N 4 , T d ) ) 10.4 ( 0.3 eV. When repeating the NRMS experiments using our tandem mass spectrometer and operating conditions, the collisional activation (CA) spectrum of N 4 •+ could be recorded, whereas we could not reproduce the neutralizationreionization spectrum reported by Cacace et al. These results suggest that although azido-nitrene was apparently generated in NRMS experiments, only a very small fraction of the N 4 neutral could effectively be reionized, and the resulting spectra could not be reproduced easily, when changing even slightly the experimental conditions.

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Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Azido-Nitrene Is Probably the N₄ Molecule Observed in Mass Spectrometric Experiments

et al. 2003

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“…Can the potential of polynitrogen compounds as high-density−high-energy materials be realized? Since N 2 is likely to be much more stable than any higher nitrogen molecule, it is understandable that the pertinent experimental investigations − are far outnumbered by the theoretical literature. − However, none of the theoretical studies have been comprehensive and systematic. The present survey compares many N n species and identifies pentazole derivatives as being the thermodynamically most stable polynitrogen compounds.…”

Section: Introductionmentioning

confidence: 99%

“…Many polynitrogen and nitrogen-rich systems have been investigated extensively at various levels of theory, e.g., N 4 , − N 4 + , N 5 - , − N 5 H, , N 6 , ,,18b, N 8 , ,,, N 10 ,21b N 20 , ,, the set of CN 7 - , N(N 3 ) 3 , HN(N 3 ) 2 , N(N 3 ) 2 - molecules and anions, and carbon/nitrogen cubanoids [(CH) 8 - n N n ] 18c…”

Section: Introductionmentioning

confidence: 99%

Besides N₂, What Is the Most Stable Molecule Composed Only of Nitrogen Atoms?

Glukhovtsev¹,

Jiao²,

Schleyer³

1996

Inorg. Chem.

255

192

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Polynitrogen molecules have been studied systematically at high levels of ab initio and density functional theory (DFT). Besides N(2), the thermodynamically most stable N(n)() molecules, located with the help of a newly developed energy increment system, are all based on pentazole units. The geometric, energetic, and magnetic criteria establish pentazole (2) and its anion (3) to be as aromatic as their isoelectronic analogues, e.g., furan, pyrrole, and the cyclopentadienyl anion. The bond lengths in 2 and 3 are equalized; both have large aromatic stabilization energies (ASE) and also substantial magnetic susceptibility exaltations (Lambda). The C(s)() symmetric azidopentazole (14), a candidate for experimental investigation, is the lowest energy N(8) isomer but is still 196.7 kcal/mol higher in energy than four N(2) molecules. Octaazapentalene (12) with 10 pi electrons also is aromatic. The D(2)(d)() symmetric bispentazole (21) is the lowest energy N(10) minimum but is 260 kcal/mol higher in energy than five N(2) molecules. For strain-free molecules, the average deviation is +/-2.6 kcal/mol between the DFT energies and those based on the increment scheme. The increment scheme also provides estimates of the strain energies of polynitrogen compounds, e.g., tetraazatetrahedrane (8, 48.2 kcal/mol), octaazacubane (11, 192.6 kcal/mol), and N(20) (27, 294.6 kcal/mol), and is useful in searching for new high-energy-high-density materials.

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“…The most striking failure is showed by the Many body perturbation theory to fourth order, which recovers a trans-planar structure. 28,30 In fact, among correlated methods, only quadratic configuration interaction ͑QCI͒ 30,31 and coupled cluster ͑CC͒ 35 can successfully describe the linear centrosymmetric structure of the complex. 12,13 Even CASSCF͑11,12͒ proved to be noncompletely successful, since the ground state was found to be linear, but not centrosymmetric.…”

Section: Doublet Ground Statementioning

confidence: 99%

The reaction N2++N2→N3++N from thermal to 25 eV

Tosi

Bassi

et al. 2001

The Journal of Chemical Physics

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Articles you may be interested inRovibrationally selected ion-molecule collision study using the molecular beam vacuum ultraviolet laser pulsed field ionization-photoion method: Charge transfer reaction of N2 +(X 2Σg +; v+ = 0-2; N + = 0-9) + Ar J. Chem. Phys. 137, 104202 (2012); 10.1063/1.4750248 Probes of spin conservation in heavy metal reactions: Experimental and theoretical studies of the reactions of Re + with H 2 , D 2 , and HD Guided ion beam studies of the reactions of Ni n + (n=2-18) with O 2 : Nickel cluster oxide and dioxide bond energies Activation of methane by size-selected iron cluster cations, Fe n + (n=2-15): Cluster-CH x (x=0-3) bond energies and reaction mechanismsThe endothermic reaction N 2 ϩ ϩN 2 →N 3 ϩ ϩN has been investigated both experimentally and by ab initio calculations. Integral cross sections are presented as a function of collision energy. For excited N 2 ϩ ions the reaction onset shifts towards lower energies, indicating that the internal energy of the reactant ions promotes the reaction. Analysis of the energy dependence of the cross section does not allow an unequivocal determination of the reaction endothermicity. However, calculations of the ground doublet surface indicate that the minimum energy path from reactants to products proceeds through strongly bent geometries, with an endothermicity equivalent to the thermodynamic value of about 5 eV. For linear geometries an additional barrier of about 1 eV is found in the product channel. The structure of N 4 ϩ in its first excited quartet state has been also calculated by ab initio methods.

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Comparative study of Møller–Plesset perturbation theory and configuration interaction theory for the structure of the N₄⁺ cation

Cited by 11 publications

References 12 publications

Azido-Nitrene Is Probably the N₄ Molecule Observed in Mass Spectrometric Experiments

Azido-Nitrene Is Probably the N₄ Molecule Observed in Mass Spectrometric Experiments

Besides N₂, What Is the Most Stable Molecule Composed Only of Nitrogen Atoms?

The reaction N2++N2→N3++N from thermal to 25 eV

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Comparative study of Møller–Plesset perturbation theory and configuration interaction theory for the structure of the N4+ cation

Cited by 11 publications

References 12 publications

Azido-Nitrene Is Probably the N4 Molecule Observed in Mass Spectrometric Experiments

Azido-Nitrene Is Probably the N4 Molecule Observed in Mass Spectrometric Experiments

Besides N2, What Is the Most Stable Molecule Composed Only of Nitrogen Atoms?

The reaction N2++N2→N3++N from thermal to 25 eV

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Comparative study of Møller–Plesset perturbation theory and configuration interaction theory for the structure of the N₄⁺ cation

Azido-Nitrene Is Probably the N₄ Molecule Observed in Mass Spectrometric Experiments

Azido-Nitrene Is Probably the N₄ Molecule Observed in Mass Spectrometric Experiments

Besides N₂, What Is the Most Stable Molecule Composed Only of Nitrogen Atoms?