Electron attachment to trans-azobenzene

Modelli, Alberto; Burrow, Paul

doi:10.1039/b908770b

Cited by 19 publications

(20 citation statements)

References 54 publications

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“…Some of our previous data indicate that DFT methods, as distinct from the semi‐empirical ones, are unable to find the bent conformation of the Q M – ion if there is an aromatic benzene ring in the molecule structure. We think that this is the problem that the other authors faced while investigating azobenzene anomalous long‐lived M – ions registered at E el = 1.0 eV. Calculations performed by MP2 and B3LYP methods in this study did not find Q M – with an energy corresponding to the experimental energy of the long‐lived M – ion peak (discrepancy reached 0.9 eV).…”

Section: Resultscontrasting

confidence: 53%

Anomalously long‐lived molecular negative ions of duroquinone

Khvostenko

Lukin

Tseplin

2012

Rapid Comm Mass Spectrometry

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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.

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Section: Resultscontrasting

confidence: 53%

Anomalously long‐lived molecular negative ions of duroquinone

Khvostenko

Lukin

Tseplin

2012

Rapid Comm Mass Spectrometry

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“…10,12,13,15 This is very unusual as the formation of metastable, i.e., detectable, molecular anions in electron attachment to isolated organic molecules in the gas phase, is generally only observed in a narrow energy range close to 0 eV. Nonetheless, a handful of exceptions have been reported, which include quinone derivatives, 11,24,25 chlorodifluoroacetic acid, 26 pyromellitic derivatives, 27 some polycyclic aromatic hydrocarbons 28,29 and a few metal complexes. 30,31 One further, remarkable exception is the formation of C 60 À in electron attachment to the highly symmetric fullerene C 60 , which is observed through resonant contributions from 0-14 eV.…”

Section: Introductionmentioning

confidence: 99%

Stabilization, fragmentation and rearrangement reactions in low-energy electron interaction with tetrafluoro-para-benzoquinone: a combined theoretical and experimental study

Ómarsson

Ingólfsson

2013

Phys. Chem. Chem. Phys.

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Quinones are a class of organic compounds whose extraordinary electron transfer properties are fundamental in ubiquitous processes such as the ATP production and the photosynthesis. Here, we report a combined theoretical and experimental study to shed some light on low-energy electron interaction with tetrafluoro-para-benzoquinone (TFQ) and para-benzoquinone (p-BQ). Similar to it's native counterpart; p-BQ, TFQ forms a metastable molecular anion at unusually high incident energies in electron attachment under single collision conditions. Transition state calculations are used for both p-BQ and TFQ to explore possible stabilization of the molecular anion through isomerization reactions, and stabilization through intramolecular vibrational energy redistribution (IVR) is discussed in relation to the electronic structure of these compounds. We also report exceptionally extensive and complex rearrangement reactions in dissociative electron attachment to TFQ and discuss possible reaction paths based on thermochemical threshold calculations. The observed fragmentation reactions can at large be described by two dissociation series, i.e., the formation of [TFQ - CO -nF](-) (n = 0, 1, 2 or 3) and [TFQ - 2CO -nF](-) (n = 0, 1, 2, 3 or 4). In the latter series we observe, at incident electron energy as low as ~0.5 eV, the excision of two CO molecules followed by recombination of the remaining moiety to form an anionic carbon chain with two terminal CF2 groups. To our knowledge such excision of two non-adjacent carbon atoms and recombination of the remaining moiety have not been observed before in low energy electron attachment.

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“…Photoelectron spectroscopy (PES) of azobenzene has been reported by Kobayashi et al 34 Electron transmission spectroscopy (ETS) data on electron attachment energies were discussed by Modelli and Burrow. 35 Proton and electron affinities were also reported. 36,37 Electron attachment to azobenzenes are also of fundamental interest in scanning tunneling microscope (STM) induced switching, in which the cis−trans isomerization of individual molecules are triggered by tunneling electrons.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The second is related to electron transmission spectroscopy (ETS) 35 and dissociative electron attachment spectroscopy (DEAS), 35 which indicated the formation of temporary anion states of gas-phase trans-AB. 35 These anion states appear as resonances in the electron-molecule scattering cross section and the associated energies correspond to vertical electron attachment processes. 35 In addition, cis−trans isomerization in the dark has been investigated for azobenzene in interaction with gold nanoparticles (AuNps).…”

Section: ■ Introductionmentioning

confidence: 99%

“…35 These anion states appear as resonances in the electron-molecule scattering cross section and the associated energies correspond to vertical electron attachment processes. 35 In addition, cis−trans isomerization in the dark has been investigated for azobenzene in interaction with gold nanoparticles (AuNps). 39−41 An electron-transfer mechanism has been proposed to explain the increase of the cis−trans isomerization rate for azobenzene in interaction with AuNps.…”

Section: ■ Introductionmentioning

confidence: 99%

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Electron Propagator Theory Approach to the Electron Binding Energies of a Prototypical Photo-Switch Molecular System: Azobenzene

Martins

Cabral

2019

J. Phys. Chem. A

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The electron binding energies for the trans and cis conformers of azobenzene (AB), a prototypical photoswitch, were investigated by electron propagator theory (EPT). The EPT results are compared with data from photoelectron and electron transmission spectroscopies and complemented by the calculation of the differences between vertical and adiabatic ionization energies and electron affinities of the AB conformers. These differences are discussed in terms of the geometry changes associated with the processes of ionization and electron attachment. The results pointed out a major difference between these processes when we compare trans-AB and cis-AB. For trans-AB, electron attachment leads to a small geometry change, whereas for cis-AB, it is the ionized structure that keeps some similarity with the neutral species. We emphasize the interest of the present results for a better understanding of recent experiments on the dark cis−trans isomerization in different environments, specifically for azobenzenes in interaction with gold nanoparticles, where the proposed cis−trans isomerization mechanism relies on electron transfer induced isomerization.

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Electron attachment to trans-azobenzene

Cited by 19 publications

References 54 publications

Anomalously long‐lived molecular negative ions of duroquinone

Anomalously long‐lived molecular negative ions of duroquinone

Stabilization, fragmentation and rearrangement reactions in low-energy electron interaction with tetrafluoro-para-benzoquinone: a combined theoretical and experimental study

Electron Propagator Theory Approach to the Electron Binding Energies of a Prototypical Photo-Switch Molecular System: Azobenzene

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