Electronic structure of nitroxyl radicals determined by means of photoelectron spectroscopy

Zykov, B. G.; Martin, Valérie; Grigoryev, I.A.

doi:10.1016/0368-2048(91)80006-g

Cited by 14 publications

(3 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The He I PE spectrum was recorded using an ES 3201 spectrometer (St. Petersburg, Russia). , A DCTB sample was placed into a direct insertion probe which was held at 140 °C. In the ionization chamber, the diffusive molecular beam crossed with the photon beam generated by the helium lamp.…”

Section: Methodsmentioning

confidence: 99%

Electron Transfer Reactivity in Matrix-Assisted Laser Desorption/Ionization (MALDI): Ionization Energy, Electron Affinity and Performance of the DCTB Matrix within the Thermochemical Framework

et al. 2006

View full text Add to dashboard Cite

DCTB [(H(3)C)(3)C-p-Ph-CH=C(CH(3))-trans-CH=C(CN)(2)] has recently advanced to the most promising matrix material for matrix-assisted laser desorption/ionization (MALDI) within material sciences. However, data that would allow the evaluation of the electron-transfer reactivity within a thermochemical framework are sparse. The present study reports the first-time determination of the ionization energy (IE) of DCTB applying photoelectron (PE) spectroscopy. The experimental IE (8.54 +/- 0.05 eV) is in excellent agreement with the theoretical value of 8.47 eV, obtained by AM1 calculations. The same level of theory determines the electron affinity (EA) as 2.31 eV. Model analytes of known thermochemistry (phenanthrene [C(14)H(10)], anthracene [C(14)H(10)] and fluorofullerene [C(60)F(46/48)]) are used to bracket the electron-transfer reactivity within DCTB-MALDI. The formation of molecular ions of these analytes either is expected or is beyond the thermochemical accessibility of the DCTB matrix.

show abstract

Section: Methodsmentioning

confidence: 99%

Electron Transfer Reactivity in Matrix-Assisted Laser Desorption/Ionization (MALDI): Ionization Energy, Electron Affinity and Performance of the DCTB Matrix within the Thermochemical Framework

et al. 2006

View full text Add to dashboard Cite

show abstract

“…Vaporisation temperatures of compounds under investigation were in the range 300-350 K. Photoelectron spectra used to guide our method of quantum-chemical calculation were obtained using a PE spectrometer (ES-3201) with a hemispherical kinetic energy analyser. 16 The details of ECNI-MS experiments, using a method developed for static mass spectrometers, 8 have been described previously.…”

Section: Methodsmentioning

confidence: 99%

Frozen shell approximation violation in negative ion formation from halogenated benzenes via dissociative attachment

Asfandiarov

Fokin

et al. 2000

Rapid Commun. Mass Spectrom.

View full text Add to dashboard Cite

A series of benzene derivatives (R(1)C(6)H(4)R(2)) has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), and PM3 quantum chemical calculations. The dissociation channel M(-.) --> Hal(-) + (M - Hal). is analysed from the point of view of symmetry conservation. Generally, a symmetry ban on dissociation may be avoided in at least two ways: (i) out-of-plane vibrations of the halogen atom in the molecular negative ion (MNI), mixing pi- and sigma-states of the anion; (ii) symmetrical in-plane vibration of the C-Hal bond, changing the order of the empty levels in the MNI with subsequent radiationless conversion into a sigma-state. Our analysis shows that neither of them provides a satisfactory explanation of the ECNI mass spectra for chlorobenzene, if one retains the usual assumption that an additional electron goes into the LUMO of the neutral molecule. Thus, it may be concluded that in this case electron capture causes a significant perturbation of the energy ordering of vacant orbitals, thus making the frozen shell approximation inapplicable. Copyright 2000 John Wiley & Sons, Ltd.

show abstract

“…The photoelectron spectrum of duroquinone was recorded with the ES‐3201 spectrometer equipped with a He(I) radiation source (21.21 eV) . The energy scale was calibrated with the lines of argon at 15.76 and 15.94 eV.…”

Section: Methodsmentioning

confidence: 99%

Anomalously long‐lived molecular negative ions of duroquinone

Khvostenko

Lukin

Tseplin

2012

Rapid Comm Mass Spectrometry

View full text Add to dashboard Cite

The problem under investigation here is establishment of mechanisms of the resonant electron capture by molecules, using the example of duroquinone (2,3,5,6-tetramethyl-1,4-benzoquinone). A solution is important because it will provide new insights into the fundamental physical laws and widespread applications in various fields like molecular nanoelectronics, touched upon herein too. Resonant electron capture (REC) in duroquinone was studied with negative ion mass spectrometry of the REC as the main method, and UV absorption and the photoelectron spectroscopy as the auxiliary ones. The latter were used to study the electronic structures of the various neutral molecular states that are the parent ones for the negative molecular ions formed by electron attachment to the molecules. B3LYP/6-311 + G(d,p) calculations were widely used throughout the study. As a result, an intensive peak of the negative molecular ions with anomalously high lifetime (200 microseconds) was registered at the attached electron energy of 1.8 eV. The ions were determined to be quartets delaying the electron autodetachment because of spin prohibition and appearing via inter-system crossing from the negative molecular ion doublets produced in the core-excited Feshbach resonances. Finally, the pattern of the REC in duroquinone was obtained for the energy region of 1-4 eV which is presented by shape resonances, core-excited Feshbach resonances and by mechanisms little-known for molecules of inter-shell resonances and the formation of ion quartets. The latter were proposed to be related to the negative differential resistance in molecular nanoelectronics.

show abstract

Electronic structure of nitroxyl radicals determined by means of photoelectron spectroscopy

Cited by 14 publications

References 7 publications

Electron Transfer Reactivity in Matrix-Assisted Laser Desorption/Ionization (MALDI): Ionization Energy, Electron Affinity and Performance of the DCTB Matrix within the Thermochemical Framework

Electron Transfer Reactivity in Matrix-Assisted Laser Desorption/Ionization (MALDI): Ionization Energy, Electron Affinity and Performance of the DCTB Matrix within the Thermochemical Framework

Frozen shell approximation violation in negative ion formation from halogenated benzenes via dissociative attachment

Anomalously long‐lived molecular negative ions of duroquinone

Contact Info

Product

Resources

About