Stereochemistry and ultraviolet spectra of simple nitrate esters

Csizmadia, Vilmos; Houlden, S. A.; Koves, Gabor; Boggs, Joan M.; Csizmadia, I. G.

doi:10.1021/jo00953a003

Cited by 19 publications

(25 citation statements)

References 5 publications

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“…Unfortunately, there are only some polyyne monoanions for which experimental PAs are available for comparison 37. The last column of the Table IV represents the experimental evaluations of PA1 of polyyne chains available at present.…”

Section: Resultsmentioning

confidence: 99%

Quantum chemical calculations of geometries and gas-phase deprotonation energies of linear polyyne chains

Mlder

Burk

Koppel

2001

Int. J. Quantum Chem.

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Section: Resultsmentioning

confidence: 99%

Quantum chemical calculations of geometries and gas-phase deprotonation energies of linear polyyne chains

Mlder

Burk

Koppel

2001

Int. J. Quantum Chem.

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“…The experimental data for the acetone concentration as a function of time and the calculated data for the photolysis of 56 ppm isopropyl nitrate in 1000 mbar of air are shown in Figure 2. The photolysis of acetone was used as reference to compare the results of the laboratory experiments with the photodissociation of the nitrates in the troposphere, since both substances absorb UV light in the same spectral region between 290 and 330 nm (Calvert and Pitts, 1966;Csizmadia et al, 1973) and the photolysis frequency of acetone can be calculated for the troposphere. The photolysis frequency of acetone was determined in the laboratory from independent experiments where only acetone diluted in air was irradiated in the reactor by using the known quantum yield of CO production, 0¢o =0.024 (Gardner et al, 1984).…”

Section: Resultsmentioning

confidence: 99%

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Becker

Wirtz

1989

J Atmos Chem

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Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295 +_ 2 K and 1000 mbar total pressure. Using a rate constant of 2.53 × 10 -12 cm 3 s -I for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10 -12 cm 3 s -1): isopropyl nitrate, 0.59___0.22; isobutyl nitrate, 1.63 ±0.20: 3-methyl-2-butyl nitrate, 1.95_+0.15; 2-methyl-l-butyl nitrate, 2.50_+0.15; 3-methyl-l-butyl nitrate, 2.55 _+0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can he used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.

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“…In accordance with most authors, the experimental spectrum is characterized by an intense π→π* absorption band centered around 6.52 eV 55,56 and a series of relatively weak bands at lower energies. For example, n→π* absorption bands were observed at 5.63 eV 55 and at 4.96 eV, 55 and another one appearing as a shoulder at ∼4.77 eV. 50,55,57−59 UV absorption cross-sections reported for EN, 50 (see also discussion in ref 58 and references therein) show that EN also absorbs light in the range of atmospheric interests with the energy smaller than 4.27 eV and wavelengths longer than 290 nm, which is likely to be associated with photolysis.…”

Section: Ethyl Nitrate As a Model Moleculementioning

confidence: 99%

Energies of Electronic Transitions of Pentaerythritol Tetranitrate Molecules and Crystals

2014

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Despite significant effort in research on energetic nitrocompounds coupled with a great interest in these materials for a range of technological and medical applications, the electronic structure of condensed energetic materials is barely studied. In this research aimed at a better understanding of the low energy absorption in the optical spectrum of nitro-compounds, the electronic structure and vertical electronic transitions of a gas-phase pentaerythritol tetranitrate (PETN) molecule and an ideal PETN crystal were explored by means of density functional theory based calculations. In accordance with most experimental observations, the optical absorption spectrum of PETN has a well-resolved intense band above 6 eV that is accompanied by a few low intensity broad bands at lower energies. Our modeling suggests that the high intensity band corresponds to a series of strong singlet−singlet transitions, while the lower energy bands are attributed to the formation of tightly bound singlet and triplet excitons. All transitions are well-localized on O−NO 2 groups of PETN. We also systematically analyze low energy excitations in other nitro-compounds, which exhibit similar patterns in the spectra even though the experimental data are incomplete at the moment. We predict that tightly bound excitons and charge transfer excitons should exist in PETN and both would trigger the nitrate decomposition, which allows for precise control of the initiation process.

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Stereochemistry and ultraviolet spectra of simple nitrate esters

Cited by 19 publications

References 5 publications

Quantum chemical calculations of geometries and gas-phase deprotonation energies of linear polyyne chains

Quantum chemical calculations of geometries and gas-phase deprotonation energies of linear polyyne chains

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Energies of Electronic Transitions of Pentaerythritol Tetranitrate Molecules and Crystals

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