Electron detachment energy

Anion photoelectron spectroscopy [37, 38] amd photodetachment techniques [39] provide accurate information on electron detachment energies of negative ions. Ten closed-shell ainions considered here exhibit sharp peaks, indicative of minor or vanishing final-state nuclear rearrangements, in their photoelectron spectra. Comparisons between theory and experiment are straiightforward, for differences between vertical and adiabatic electron detachment energies (VEDEs and AEDEs, respectively) are small. 

Another approach of this kind uses the approximate Brueckner orbitals from a so-called Brueckner doubles, coupled-cluster calculation [39, 40]. Methods of this kind are distinguished by their versatility and have been applied to valence ionization energies of closed-shell molecules, electron detachment energies of highly correlated anions, core ionization... 

Calculation of ionization energy (electron detachment energy) of the anionic species using P3 method with 6-311++G(2df,2p) basis set. 

Doublet reference states. Some patterns emerge from the calculations with doublet reference states. Table 5.9 presents a summary of all cases involving transitions between singlets and doublets. Ionization energy calculations perform well when a doublet reference state is used. However, electron affinity calculations are advisable only when the doublet reference state is cationic. Even here, it is preferable to reverse the roles of initial and final states by choosing the closed-shell neutral as the reference state in an ionization energy calculation. The P3 method is not suitable for attachment of an electron to a neutral doublet reference state to form a closed-shell anion. It is preferable to choose the anion as the reference state for a P3 calculation of an electron detachment energy. Results for triplets are unpredictable at best. 

V.V. Zakjevskii et al., Base and phosphate electron detachment energies of deoxyribonu-cleotide anions. J. Am. Chem. Soc. 128, 13350-13351 (2006)... 

V.V. Zakjevskii et al., Electron propagator studies of vertical electron detachment energies and isomerism in purinic deoxyribonucleotides. Int. J. Quantum Chem. 107, 2266-2273 (2007)... 

Table 5 8 3. Experimental and calculated vertical electron detachment energies (VDEs, in kJ mol 1) for LiAl, NaAl, and CuAl ...

Tab. 17.1. The relative stability, vertical electron detachment energy, binding energy of CO (with O2 preadsorbed) and binding energy of O2 (with CO preadsorbed) for the five structures (a)-(e) ofAu2C03, shown in Figure 17.2C.

Table 4 Vertical electron-detachment energies (in eV), with different approximations, along the reaction path...

TaF5 and TaFxCl5 x have been identified in the gas phase by mass spectrometric detection of their primary ions.220 The crystal structure of the salt [Ph3PMe][TaF6] has been reported.403 The gas-phase molecular structure, vibrational frequencies, and vertical electron detachment energy for [rl aF6] were examined theoretically at HF, MP2, and DFT levels of theory.404... 

Keywords electron propagator quasiparticle approximations renormalized approximations quasiparticle virtual orbitals C60 fullerene ionization energies correlation states nucleotide electron detachment energies... 

The adiabatic electron detachment energies of all 16 possible monoanionic dinucleotides have been tabulated in [50], but no VDE values were reported. The spectra of a few dinucleotides were displayed in the same publication. These included the spectra of dAA, dCC-, dGG-, dTT, dAG, dCG, dGA-, and dTG-. With some careful inspection of the onsets, it is possible to estimate VDEs from these spectra. 

Fig. 1.16. The graph presents a comparison of theoretical and experimental vertical electron detachment energies (VDEs) for Aun in = 4-14). The optimized ground state structures (labeled A for each size) and close lying low-energy isomers are also displayed [120]. A change from planar geometry to SD-structural motifs is apparent between Aui2 and Auis ...

N. Mikami, Infrared spectroscopic evidence for protonated water clusters forming nanoscale cages, Science 304, 1134-1137 (2004). (e) S. B. Suh, H. M. Lee, J. Kim, J. Y. Lee, and K. S. Kim, Vibrational spectra and electron detachment energy of the anionic water hexamer,... 

Ab initio Electron Propagator Calculations on Electron Detachment Energies of Fullerenes, Macrocyclic Molecules, and Nucleotide Fragments... 

As an illustration consider C=C=C=C which is a triplet ( Sg ) with a -It HOMO occupied by two electrons of parallel spin. Table 21 displays results obtained with several different levels of correlation and basis sets." There are actually three different quantities that can be computed the vertical electron detachment energy (VEDE, energy to eject electron at the geometry of the anion) the adiabatic electron affinity (AEA, when the neutral M is allowed to relax to its optimum geometry), and the vertical electron affinity (VEA, where the geometry of the neutral is assumed for the anion). 

Table 21 Calculated Electron Affinities and Electron Detachment Energies (eV) of Linear C4 and C4 ...

TTie vertical electron detachment energy (VDE) is calculated as the total energy difference between the anionic and neutral clusters, both taken in the anionic optimized geometry without die ZPVE. The adiabatic electron affinity (EAa) and ionization energy (lEa) are calculated as the total energy difference between the anionic and cationic clusters, respectively, and the parent neutral cluster in their optimized geometries. 

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