Vertical electron detachment energies VDEs

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

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 ...

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. 

The ensemble of initial conditions can be characterized by the Franck-Condon transition probabilities and visualized in terms of the abundances of the vertical electron detachment energies (VDE s) between the Ag4 and Ag species. The histograms of the VDE s for three ensembles of different temperatures are shown in Fig. 7. For the ensemble generated for T=50 K,... 

Table 21-1. Values of stabilization energy (Estab), stabilization free energy (Gslab), their relative values (AE and AG calculated with respect to the Watson-Crickpair), electron vertical detachment energy (VDE) and adiabatic electron binding energy (EBE0) for the anionic adenine-thymine and 9-methyladenine-1-methylthymine complexes calculated at the B3LYP/6-31+G level. (Table 1 of ref. [49]. Reprinted with permission. Copyright 2005 American Chemical Society.)...

Table 21-2. Relative electronic energies and free energies (AE and AG) calculated with respect to the aHX(AT) or aHX(AT)-SPT anion together with the adiabatic electron affinities (AEAG) and electron vertical detachment energies (VDE) for the anionic HX(AT) complexes predicted at the B3LYP/6-31+G" level. AE and AG in kcal/mol AEAG and VDE in eV...

Concerning the shift in the energy position of the NIS, it is instructive to refer to Fig. 16 which shows schematically the vertical attachment energy (VAE), the electron affinity (EA) and the vertical detachment energy (VDE) and to Fig. 17 which shows schematically the increase in the VAE (less negative) and the increase in the EA (more positive) in going from dilute gas to the liquid. 

Fig. 16. Schematic potential energy diagrams for AX and AX indicating the electron affinity EA, the vertical attachment energy VAE, and the vertical detachment energy VDE. 

Potential energy surfaces (PES) of an anion formation (M ) after electron (e ) attachment to the neutral molecule (M). When the energy of an anion (M ) lies below the neutral molecule, positive electron affinity Is observed [left) otherwise the molecule is said to have negative electron affinity right). Energy changes shown for an electron attachment or detachment event are (1) the vertical electron affinity (VEA), (2) the adiabatic electron affinity (AEA), and (3) the vertical detachment energy (VDE). The VDE and VEA impose the upper and lower bounds to AEA... 

Figure 20-3. Electron binding energies for molecule M in anionic state are defined pictorially in a representation of the potential energy surfaces of the neutral molecule (M) and anion radical (M ) with the lowest vibration energy level shown for each. During a vertical process, the geometry remains unchanged but for the adiabatic process structural relaxation occurs. Thus the VDE (vertical detachment energy) and VEA (vertical electron affinity) represent the upper and lower bounds to the adiabatic electron affinity (AEA)...

ADE = adiabatic detachment energies ESC A = electron spectroscopy for chemical analysis HOMO = highest occupied molecular orbitals MAES = metastable atom electron spectroscopy MIES = metastable ionization electron spectroscopy OAT = oxygen atom transfer PES = photoelectron spectra PEI = pulsed field ionization PIES = Penning ionization electron spectroscopy QM = quantum-mechanical REMPI = resonantly enhanced multiphoton ionization SC = semiclassical VDE = vertical detachment energies XPS = x-ray photoelectron spectroscopy ZEKE = zero electron kinetic energy Cp = cyclopentadienyl, Ph = phenyl, CeHs Tp =... 

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