A Gas-Phase and Matrix Isolation Study of the Equilibrium CH3ONO (cis) .dblarw. CH3ONO (trans) by FTIR Spectroscopy

Bodenbinder, Matthias; Ulic, Sonia E.; Willner, Helge

doi:10.1021/j100077a004

Cited by 63 publications

(78 citation statements)

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“…The band is assigned to the terminal NO stretch of the anti-conformer of methyl nitrite [17]. However, no such bleach is seen at 1615 cm -1 (beyond our baseline noise levels, which are 10% of the amplitude of the 1670 cm -1 bleach feature) for the corresponding vibrational band of the syn-conformer.…”

Section: Resultsmentioning

confidence: 51%

“…Syn and anti-conformers account for 60% and 40% of ground state MeONO molecules respectively at room temperature [17]. The anti-conformer lies 290 cm -1 higher in energy than the syn form [17], and interconversion is hindered by a ~3500 cm -1 energy barrier [18].…”

mentioning

confidence: 99%

“…The anti-conformer lies 290 cm -1 higher in energy than the syn form [17], and interconversion is hindered by a ~3500 cm -1 energy barrier [18]. The contributions of these two conformers to the structure in the 1 ← 0 UV band has been the subject of prior controversy.…”

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confidence: 99%

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Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Coulter

Grubb

Orr-Ewing

2017

Chemical Physics Letters

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms UV excitation in the structured S1  S0 absorption band induces dissociation, with geminate recombination and vibrational cooling of syn and anti-conformers of methyl nitrate on a timescale of ~56 ps. Solvent-induced vibrational cooling favours relaxation to the higher-energy anti-conformer on entropic grounds, and subsequent inter-conversion to the lower-energy synconformer is prevented by a 3500 cm -1 barrier. UV excitation to the 2 state produces a transient electronic absorption band resembling the absorption spectrum of NO2.

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Section: Resultsmentioning

confidence: 51%

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confidence: 99%

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Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Coulter

Grubb

Orr-Ewing

2017

Chemical Physics Letters

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“…1). The smaller members of this family of molecules have been the subject of several experimental studies [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19], and the most recent results consistently demonstrate that the cis conformer of methyl nitrite corresponds to the most stable form [8][9][10][11][12][13][14][15][17][18][19]. The gas-phase AHtrans_cis, Agtrans_ci s and AGtrans_ci s obtained by 1H NMR spectroscopy * Corresponding author.…”

Section: Introductionmentioning

confidence: 99%

“…This fact justifies the interest in performing additional structural studies on methyl nitrite by using a more systematic theoretical approach carried out at a higher level of theory. The vibrational spectrum of methyl nitrite has also been studied by several authors under a series of different experimental conditions (gas phase [1,4,9,11,13,[17][18][19], pure liquid [18], solid [18], solution [4], noble-gas matrix [ 12,13,17], supersonic jet [8]). In addition, the infrared spectra of methyld3 nitrite in both the gaseous and solid phases [13,18], and isolated in an argon matrix [13] have also been reported.…”

Section: Introductionmentioning

confidence: 99%

Vibrational spectra and structure of the cis and trans conformers of methyl nitrite: an ab initio MO study

Silva

Costa

Ramos

et al. 1996

Journal of Molecular Structure: THEOCHEM

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The vibrational and conformational properties exhibited by nethyl nitrite (CH3ON~O) were studied by ab initio MO methods (HF-SCF and MP2) using both the 6-31G and 6-311G basis sets without or with the inclusion of diffuse and/or polarization functions. Fully optimized geometries, relative stabilities, dipole moments and harmonic force fields for both the cis and trans conformers of this molecule were determined and the results compared with available experimental data. In agreement with the experimental results, the calculations involving polarization functions at the MP2 level of theory indicate that the most stable conformer of methyl nitrite is the planar cis conformer, where the methyl group is eclipsing the N--~-O bond, while the trans form was predicted to have a higher energy than this form by about 4 kJ mol 1. The conformational dependence of some relevant structural parameters was used to characterize the most important intramolecular interactions present in the studied conformers, and their calculated infrared spectra were used to review previous assignments of the experimentally observed bands for both the normal and deuterated (CDaON~-O) species. Chemometrics methods (principal components and two-level factorial designing) were used both to analyze the effect of changing the basis set and level of theory used to perform the calculations, and to aid comparison between the experimental and calculated vibrational spectra.

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Phosphorus Analogues of Methyl Nitrite and Nitromethane: CH₃OPO and CH₃PO₂

Zhao¹,

Chu²,

Rauhut³

et al. 2019

Angewandte Chemie

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Methoxyphosphinidene oxide (CH3OPO) and isomeric methyldioxophosphorane (CH3PO2) are key intermediates in the degradation of organophosphorus compounds (OPCs). Unlike the nitrogen analogues CH3ONO and CH3NO2, the experimental data for these two prototypical OPCs are scarce. By high‐vacuum flash pyrolysis (HVFP) of the diazide CH3OP(O)(N3)2 at 1000 K, the cis and trans conformers of CH3OPO have been generated in the gas phase and subsequently isolated in cryogenic Ar and N2 matrices for IR spectroscopic characterization. Upon 266 nm laser irradiation of CH3OPO, cis→trans conformational conversion occurs with concurrent isomerization to CH3PO2. The spectroscopic identification of CH3OPO and CH3PO2 is supported by D‐, 13C‐, and 18O‐isotope labeling and quantum chemical calculations at the CCSD(T)‐F12a/cc‐pVTZ‐F12 level using configuration‐selective vibrational configuration interaction (VCI).

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A Gas-Phase and Matrix Isolation Study of the Equilibrium CH3ONO (cis) .dblarw. CH3ONO (trans) by FTIR Spectroscopy

Cited by 63 publications

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Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Vibrational spectra and structure of the cis and trans conformers of methyl nitrite: an ab initio MO study

Phosphorus Analogues of Methyl Nitrite and Nitromethane: CH₃OPO and CH₃PO₂

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A Gas-Phase and Matrix Isolation Study of the Equilibrium CH3ONO (cis) .dblarw. CH3ONO (trans) by FTIR Spectroscopy

Cited by 63 publications

References 0 publications

Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Vibrational spectra and structure of the cis and trans conformers of methyl nitrite: an ab initio MO study

Phosphorus Analogues of Methyl Nitrite and Nitromethane: CH3OPO and CH3PO2

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Phosphorus Analogues of Methyl Nitrite and Nitromethane: CH₃OPO and CH₃PO₂