The C–N dissociation energies of nitrobenzene and nitrotoluene radical anions and neutrals

Pruitt, Carrie Jo M.; Goebbert, Daniel J.

doi:10.1016/j.cplett.2013.06.050

Cited by 14 publications

(9 citation statements)

References 40 publications

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“…The calculated energy difference for the loss of NO 3 – is 1.99 eV whereas the energy difference for the loss of NO 2 • is 2.23 eV. Calculated energy differences are greater than the experimental appearance energies, about 1.3 eV for both ions, Figure a, because the internal energy of Al(NO 3 ) 4 – from electrospray ionization reduces the energy required for fragmentation. ,,, The elimination of NO 3 – yields an undetectable neutral aluminum complex, this this reaction is ignored in the following discussion. The O 2 N–O – bond energy of the isolated nitrate ion is 4.69 eV .…”

Section: Resultsmentioning

confidence: 90%

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Gas-Phase Fragmentation of Aluminum Oxide Nitrate Anions Driven by Reactive Oxygen Radical Ligands

et al. 2016

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Gas-phase metal nitrate anions are known to yield a variety of interesting metal oxides upon fragmentation. The aluminum nitrate anion complexes, Al(NO3)4(-) and AlO(NO3)3(-) were generated by electrospray ionization and studied with collision-induced dissociation and energy-resolved mass spectrometry. Four different decomposition processes were observed, the loss of NO3(-), NO3(•), NO2(•), and O2. The oxygen radical ligand in AlO(NO3)3(-) is highly reactive and drives the formation of AlO(NO3)2(-) upon loss of NO3(•), AlO2(NO3)2(-) upon NO2(•) loss, or Al(NO2)(NO3)2(-) upon abstraction of an oxygen atom from a neighboring nitrate ligand followed by loss of O2. The AlO2(NO3)2(-) fragment also undergoes elimination of O2. The mechanism for O2 elimination requires oxygen atom abstraction from a nitrate ligand in both AlO(NO3)3(-) and AlO2(NO3)2(-), revealing the hidden complexity in the fragmentation of these clusters.

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Section: Resultsmentioning

confidence: 90%

“…− from electrospray ionization reduces the energy required for fragmentation. 14,15,21,28 The elimination of NO 3…”

Section: Experimental Methodsmentioning

confidence: 99%

Gas-Phase Fragmentation of Aluminum Oxide Nitrate Anions Driven by Reactive Oxygen Radical Ligands

et al. 2016

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“…In Table 1, we show how the calculated value of the C-NO 2 BDE for nitrobenzene converges by increasing the size of the basis set. This value has been measured to be 298.7 kJ mol −1 [58] and 314.5 kJ mol −1 [59].…”

Section: Density Functional Theory Calculationsmentioning

confidence: 92%

Models for predicting impact sensitivity of energetic materials based on the trigger linkage hypothesis and Arrhenius kinetics

et al. 2020

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In order to predict the impact sensitivity of high explosives, we designed and evaluated several models based on the trigger linkage hypothesis and the Arrhenius equation. To this effect, we calculated the heat of detonation, temperature of detonation, and bond dissociation energy for 70 energetic molecules. The bond dissociation energy divided by the temperature of detonation proved to be a good predictor of the impact sensitivity of nitroaromatics, with a coefficient of determination (R2) of 0.81. A separate Bayesian analysis gave similar results, taking model complexity into account. For nitramines, there was no relationship between the impact sensitivity and the bond dissociation energy. None of the models studied gave good predictions for the impact sensitivity of liquid nitrate esters. For solid nitrate esters, the bond dissociation energy divided by the temperature of detonation showed promising results (R2 = 0.85), but since this regression was based on only a few data points, it was discredited when model complexity was accounted for by our Bayesian analysis. Since the temperature of detonation correlated with the impact sensitivity for nitroaromatics, nitramines, and nitrate esters, we consider it to be one of the leading predictive factors of impact sensitivity for energetic materials.

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“…Several experimental factors contributing to deviation from theory were described in the methods, but the internal energy of the precursor ion is a major of source error. The precursor ion contains a substantial, but unknown, amount of internal energy above the zero-point level that accounts for the discrepancy between experiment and theory. − , …”

Section: Discussionmentioning

confidence: 99%

“…The precursor ion contains a substantial, but unknown, amount of internal energy above the zero-point level that accounts for the discrepancy between experiment and theory. [54][55][56][57]59 Theory predicts the energy for the [MnO…”

Section: Discussionmentioning

confidence: 99%

Formation of a Spin-Forbidden Product, ¹[MnO₄]⁻, from Gas-Phase Decomposition of ⁶[Mn(NO₃)₃]⁻

et al. 2016

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The manganese nitrate complex, [Mn(NO3)3](-), was generated via electrospray ionization and studied by tandem quadrupole mass spectrometry. The complex is assumed to decompose into [MnO(NO3)2](-) by elimination of NO2(•). The [MnO(NO3)2](-) product undergoes elimination of NO2(•) to yield [MnO2(NO3)](-), or elimination of NO(•) to yield [MnO3(NO3)](-). Both [MnO2(NO3)](-) and [MnO3(NO3)](-) yield [MnO4](-) via the transfer of oxygen atoms from the remaining nitrate ligand. The mechanism of permanganate formation is interesting because it can be generated through two competing pathways, and because the singlet ground state is spin-forbidden from the high-spin sextet [Mn(NO3)3](-) precursor. Theory and experiment suggest [MnO2(NO3)](-) is the major intermediate leading to formation of [MnO4](-). Theoretical studies show crossing from the high-spin to low-spin surface upon neutral oxygen atom transfer from the nitrate ligand in [MnO2(NO3)](-) allows formation of (1)[MnO4](-). Relative energy differences for the formation of (1)[MnO4](-) and (1)[MnO3](-) predicted by theory agree with experiment.

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The C–N dissociation energies of nitrobenzene and nitrotoluene radical anions and neutrals

Cited by 14 publications

References 40 publications

Gas-Phase Fragmentation of Aluminum Oxide Nitrate Anions Driven by Reactive Oxygen Radical Ligands

Gas-Phase Fragmentation of Aluminum Oxide Nitrate Anions Driven by Reactive Oxygen Radical Ligands

Models for predicting impact sensitivity of energetic materials based on the trigger linkage hypothesis and Arrhenius kinetics

Formation of a Spin-Forbidden Product, ¹[MnO₄]⁻, from Gas-Phase Decomposition of ⁶[Mn(NO₃)₃]⁻

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The C–N dissociation energies of nitrobenzene and nitrotoluene radical anions and neutrals

Cited by 14 publications

References 40 publications

Gas-Phase Fragmentation of Aluminum Oxide Nitrate Anions Driven by Reactive Oxygen Radical Ligands

Gas-Phase Fragmentation of Aluminum Oxide Nitrate Anions Driven by Reactive Oxygen Radical Ligands

Models for predicting impact sensitivity of energetic materials based on the trigger linkage hypothesis and Arrhenius kinetics

Formation of a Spin-Forbidden Product, 1[MnO4]−, from Gas-Phase Decomposition of 6[Mn(NO3)3]−

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Formation of a Spin-Forbidden Product, ¹[MnO₄]⁻, from Gas-Phase Decomposition of ⁶[Mn(NO₃)₃]⁻