Ions, isolated, ionization potential

The direct access to the electrical-energetic properties of an ion-in-solution which polarography and related electro-analytical techniques seem to offer, has invited many attempts to interpret the results in terms of fundamental energetic quantities, such as ionization potentials and solvation enthalpies. An early and seminal analysis by Case etal., [16] was followed up by an extension of the theory to various aromatic cations by Kothe et al. [17]. They attempted the absolute calculation of the solvation enthalpies of cations, molecules, and anions of the triphenylmethyl series, and our Equations (4) and (6) are derived by implicit arguments closely related to theirs, but we have preferred not to follow their attempts at absolute calculations. Such calculations are inevitably beset by a lack of data (in this instance especially the ionization energies of the radicals) and by the need for approximations of various kinds. For example, Kothe et al., attempted to calculate the electrical contribution to the solvation enthalpy by Born s equation, applicable to an isolated spherical ion, uninhibited by the fact that they then combined it with half-wave potentials obtained for planar ions at high ionic strength. 

Another consequence of the stronger interactions upon ionization is that the equilibrium geometry of the ionized complex may differ signihcantly from that of the neutral states. Broadened ionization onsets are frequently attributed to the spectral superposition of ionization into several vibrational levels for which Franck-Condon factors are more favorable. As a result, the adiabatic ionization potential may be considerably lower than the vertical potential, and the observed ionization onsets may occur above the adiabatic potential. Another factor to be considered is the conformation-dependent efifect, due to the different conformations of the solvent molecules. The most populated form of a complex may involve a less stable form of the solvent. After photoionisation, the lowest-energy dissociation channel in the complex ion leads to the most stable form of isolated solvent, which has to be taken into account for the estimate of the binding energy. 

It was also observed, in 1973, that the fast reduction of Cu ions by solvated electrons in liquid ammonia did not yield the metal and that, instead, molecular hydrogen was evolved [11]. These results were explained by assigning to the quasi-atomic state of the nascent metal, specific thermodynamical properties distinct from those of the bulk metal, which is stable under the same conditions. This concept implied that, as soon as formed, atoms and small clusters of a metal, even a noble metal, may exhibit much stronger reducing properties than the bulk metal, and may be spontaneously corroded by the solvent with simultaneous hydrogen evolution. It also implied that for a given metal the thermodynamics depended on the particle nuclearity (number of atoms reduced per particle), and it therefore provided a rationalized interpretation of other previous data [7,9,10]. Furthermore, experiments on the photoionization of silver atoms in solution demonstrated that their ionization potential was much lower than that of the bulk metal [12]. Moreover, it was shown that the redox potential of isolated silver atoms in water must... 

Metallocenes are useful electron donors as judged by their low (vertical) ionization potentials in the gas phase and oxidation potentials in solution (see Table 2). In fact, the electron-rich (19 e ) cobaltocene with an oxidation potential of E°ox = -0.9 V relative to the SCE [45] is commonly employed as a very powerful reducing agent in solution. Unlike the alkylmetals (vide supra), the HOMOs of metallocenes reside at the metal center [46] which accounts for two effects (i) Removal of an electron from the HOMO requires minimal reorganization energy which explains the facile oxidative conversion from metallocene to metallocenium. (ii) The metal-carbon bonding orbitals are little affected by the redox process, and thus the resulting metallocenium ions are very stable and can be isolated as salts. 

Photoelectron spectra of benzothiete 209, the ketene derivative 210, (not isolated), and the naphthothiete 205 have been obtained and vertical ionization potentials reported. The unstable thiolactone 211 shows a carbonyl absorption at 1803 cm . ° The mass spectra of thietes usually show the molecular ion minus a hydrogen atom or other group as the most abundant species, thus suggesting the possible formation of a 4 -electron cation, for example, 212. ° ... 

The energy required to remove an electron from an isolated atom to infinity is called the ionization potential I, that of eliminating the -th electron is called the -th ionization potential (/ ). Ionization of atoms (or molecules) can be caused by a collision with an electron or another ion or molecule, by strong electric fields, or by thermal emission of electrons. Spectroscopic methods can determine the first ionization potentials (/i) of atoms or molecules with the accuracy of 0.01-0.001 eV, and occasionally as high as 0.0005 eV. For successive ionization potentials the errors increase to tenths or even units of eV [1 ]. The values of / for valence-shell electrons are listed in Table 1.1. 

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