Gas-Phase Generation and Photoelectron Spectra of Reactive Unsubstituted Cycloalkenethiones

Chrostowska, Anna; Miqueu, Karinne; Pfister‐Guillouzo, G.; Briard, Emmanuelle; Levillain, Jocelyne; Ripoll, Jean‐Louis

doi:10.1006/jmsp.2000.8273

Cited by 19 publications

(3 citation statements)

References 13 publications

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“…First vertical ionization energy ‫ܧܫ(‬ ଵ,௩ ) was calculated with ∆SCF-DFT, as a difference between ground states of cation and neutral ‫ܧܫ(‬ ଵ,௩ = ‫ܧ‬ ௧ − ‫ܧ‬ ௨௧ ) at the same geometry (of neutral system). [24][25][26] The TDDFT [27][28][29][30] approach was used for the calculation of higher ionization energies in combination with Δ SCF-DFT method. 29,31,32 The vertical ionization energies were also calculated at the ab initio level according to OVGF 33,34 and SAC-CI [35][36][37] (Symmetry Adapted Cluster/Configuration Interaction) methods.…”

Section: Methodsmentioning

confidence: 99%

“…Possible conformers were investigated and optimized to find the most stable one. First vertical ionization energy ( IE 1, v ) was calculated with ΔSCF-DFT, as a difference between ground states of cation and neutral ( IE 1, v = E cation – E neutral ) at the same geometry (of neutral system). − The TDDFT − approach was used for the calculation of higher ionization energies in combination with ΔSCF-DFT method. ,, The vertical ionization energies were also calculated at the ab initio level according to OVGF , and SAC–CI − (symmetry adapted cluster/configuration interaction) methods. We also use Koopmans’ theorem for a rough estimation of IE, within frozen orbital approximation ( IE 1 = −ε HOMO KS ).…”

Section: Methodsmentioning

confidence: 99%

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Isoselenocyanates versus Isothiocyanates and Isocyanates

et al. 2018

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Alkyl and aryl isoselenocyanates are well known intermediates in the synthesis of various organoselenium compounds, but the knowledge of the physicochemical properties of simple unsaturated derivatives is still fragmentary. Vinyl-, 2-propenyl-, and cyclopropyl isoselenocyanates have been prepared by reaction of selenium in powder with the corresponding isocyanides. The isoselenocyanates of this series, with a variable distance between the N═C═Se group and the unsaturated or pseudounsaturated group, have been studied by UV-photoelectron spectroscopy and quantum-chemical calculations. For each of these three isoselenocyanates, the exploration of conformers and geometrical optimization always converge toward only one local minimum. The vinyl and cyclopropyl derivatives are characterized by similar order of magnitude of interactions between the NCSe group and the substituent, while for allylic compound two noninteracting moieties should be considered. The same conclusions were obtained for vinylic and cyclopropylic sulfur and oxygen derivatives. Thus the type and extent of interactions between the N═C═X (X = O, S, Se) group and an unsaturated (vinyl, allyl, or cyclopropyl) moiety are now clarified.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Isoselenocyanates versus Isothiocyanates and Isocyanates

et al. 2018

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“…IEs were calculated on the most stable conformer (see the SI) with DSCF/TD-DFT (IE = E cation ÀE neutral ). [38][39][40] TD-DFT [41][42][43] is afirst-principles method for the calculation of excitation energies within ad ensity functional context taking into account the low-lying ion calculated by the DSCF method. The IEs were also calculated at the ab initio level according to OVGF, [44,45] SAC-CI (Symmetry Adapted Cluster/Configuration Interaction) [46] and P3 [47] (Partial Third Order Method).…”

Section: Computational Detailsmentioning

confidence: 99%

The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds

et al. 2015

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Cyanohydrins are usually formed by addition of hydrogen cyanide to aldehydes or ketones while the elimination of HCN from cyanohydrins is easily observed upon heating. The low thermal stability of these highly boiling compounds leads to difficult studies in the gas phase where partial or complete decomposition is usually observed. Consequently, the reported physicochemical properties of such compounds in the gas phase are still scarce. Keeping with this, four simple cyanohydrins, the glycolonitrile and methyl, vinyl and ethynyl derivatives, have been selected. These are possible candidates for the Interstellar Medium, where the corresponding aldehydes and HCN have been detected, and could have played an important role in prebiotic chemistry, as already proposed for some of them. Three well-suited spectroscopic techniques, namely, UV photoelectron, infrared, and Raman spectroscopies, in tandem with quantum calculations, have been chosen for the structure analysis. Photoelectron spectroscopy, successfully performed with gaseous compounds, provides the first comparative study on cyanohydrins in the gas phase.

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Ionization potentials of heteroalkenes: a comparative study

Chrostowska

Lemierre

Dargelos

et al. 2004

Applied Organom Chemis

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Methanimine, methylenephosphine and methylenearsine have been prepared in the gas phase and the gaseous flow has been analyzed by spectroscopy. Photoelectron spectra have been recorded and we report here a comparative study on these spectra. This comparison has been extended to the corresponding derivatives with a triple bond: hydrogen cyanide and methylidynephosphine. Estimation by theoretical calculations of the ionization potentials of the unknown methylidynearsine has been proposed.

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Gas-Phase Generation and Photoelectron Spectra of Reactive Unsubstituted Cycloalkenethiones

Cited by 19 publications

References 13 publications

Isoselenocyanates versus Isothiocyanates and Isocyanates

Isoselenocyanates versus Isothiocyanates and Isocyanates

The Electronic Structure of Some Cyanohydrins—A Spectroscopically Under‐Investigated Family of Compounds

Ionization potentials of heteroalkenes: a comparative study

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