Anion A–• HX Clusters with Reduced Electron Binding Energies: Proton vs Hydrogen Atom Relocation upon Electron Detachment

2014 ◽  
Vol 136 (49) ◽  
pp. 17332-17336 ◽  
Author(s):  
Xue-Bin Wang ◽  
Steven R. Kass
Keyword(s):  
Hydrogen Atom ◽  
Binding Energies ◽  
Electron Detachment ◽  
Electron Binding Energies ◽  
Electron Binding

THE PERFORMANCE OF SELECTED AB INITIO METHODS IN ESTIMATING ELECTRON BINDING ENERGIES OF SUPERHALOGEN ANIONS

2011 ◽  
Vol 10 (01) ◽  
pp. 93-109 ◽  
Author(s):  
CELINA SIKORSKA ◽  
DOROTA IGNATOWSKA ◽  
SYLWIA FREZA ◽  
PIOTR SKURSKI
Keyword(s):  
Ab Initio ◽  
Binding Energies ◽  
Basis Sets ◽  
Electron Detachment ◽  
Hartree Fock ◽  
Moller Plesset ◽  
Very High ◽  
Outer Valence ◽  
Electron Binding Energies ◽  
Electron Binding

The capability of reproducing the vertical electron detachment energies (VDE) of four representative superhalogen anions was tested using the selected ab initio (Hartree-Fock (HF), second, third, and fourth-order Møller-Plesset perturbational scheme (MP2, MP3, MP4), coupled-cluster CCSD(T), and outer valence Green function (OVGF)) methods together with the variety of one-electron basis sets. Certain theoretical treatments (e.g. MP2/aug–cc–pVTZ and MP2/6-311+G(3df)) were found to be satisfactory for preliminary estimates of electron binding energies of superhalogen anions, whereas the use of the OVGF/6-311+G(3df) approach has been proven to assure a very high accuracy of the results.

Microsolvation effects on the electron binding energies of halide anions

2013 ◽  
Vol 112 (3-4) ◽  
pp. 332-339 ◽  
Author(s):  
O. Dolgounitcheva ◽  
V.G. Zakrzewski ◽  
L. Streit ◽  
J.V. Ortiz
Keyword(s):  
Binding Energies ◽  
Halide Anions ◽  
Electron Binding Energies ◽  
Electron Binding

scholarly journals Electronic Spectroscopy of Isolated DNA Polyanions

2018 ◽  
Author(s):  
Steven Daly ◽  
Massimiliano Porrini ◽  
Frédéric Rosu ◽  
Valerie Gabelica
Keyword(s):  
Gas Phase ◽  
Absorption Spectra ◽  
Ion Mobility ◽  
Photoelectron Spectroscopy ◽  
Binding Energies ◽  
Action Spectroscopy ◽  
Action Spectra ◽  
Vis Spectroscopy ◽  
Electron Binding Energies ◽  
Electron Binding

In solution, UV-vis spectroscopy is often used to investigate structural changes in biomolecules (i.e., nucleic acids), owing to changes in the environment of their chromophores (i.e., the nucleobases). Here we address whether action spectroscopy could achieve the same for gas-phase ions, while taking the advantage of additional mass spectrometry and ion mobility separation of complex mixtures. We therefore systematically studied the action spectroscopy of homo-base 6-mer DNA strands (dG6, dA6, dC6, dT6), and discuss the results in light of gas-phase structures validated by ion mobility spectrometry and infrared ion spectroscopy, and in light of electron binding energies measured by photoelectron spectroscopy, and calculated electronic photo-absorption spectra. When UV photons interact with oligonucleotide polyanions, two main actions may take place: (1) fragmentation and (2) electron detachment. The action spectra reconstructed from fragmentation follow the absorption spectra well, and result from multiple cycles of absorption and internal conversion. The action spectra reconstructed from the electron photodetachment (EPD) efficiency reveal interesting phenomena: EPD depends on the charge state in a manner depending on electron binding energies, and is particularly efficient for purines but not pyrimidines. EPD thus reflects not only absorption, but also particular relaxation pathways of the electronic excited states. As these pathways lead to photo-oxidation, their investigation on model gas-phase systems may prove useful to elucidate mechanisms of photo-oxidative damages, which are linked to mutations and cancers.

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