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lence electronic transistors are most likely to occur from the le' orbitals, i.e., the C-H bonds, to the half-filled 2a[ orbital. Concluding RemarksExtensive RHF calculations using a large CGTO basis set indicate that the equilibrium geometry for the methyl radical is planar. This was clearly shown by computing an extensive part of the potential surface for changes in the pyramidal bending angle and C-H bond lengths. The calculations also reveal that the theoretical predictions for the geometry of the methyl radical, at least using SCF methods, are not dependable when small basis sets are employed. Another possible source of confusion over the geometry of the methyl radical results from the analytical fitting of the very flat potential surface about the planar geometry. An extensive surface should be calculated and carefully fitted to obtain the correct equilibrium geometry.An atom superposition and electron delocalization molecular orbital study has been made of the adsorption and reaction of single HsO+, H20, and OH molecules on an Fe5 model of an iron electrode over a potential range of 4 V. Changes in electrode potential are simulated by shifting the Fe valence band by means of increases or decreases in Fe atom ionization potentials. Over a range of about 2 V, conditions are identified corresponding to H30+ or H20 reduction at the cathodic end of the range and OH oxidation at the anodic end, corresponding to first steps in H2 and O2 formation. Throughout the intermediate range H20 is found to dehydrogenate, creating a surface OH layer which becomes increasingly more stable and positively charged as the potential goes anodic (eventually being oxidized to form FeO, or 02). This OH layer corresponds to initial stages of anodic passive film formation on iron.It is fiist shown that the ligand field parameters, describing a given Ni(II)-ligand interaction, depend significantly on whether the complex is high spin ( S = 1) or low spin ( S = 0). The low-spin u and T parameters are approximately 40% larger than the high-spin parameters. Using this result, it is possible to analyze a number of photoreactions of Ni(I1) compounds. A rationalization is offered for singlet == triplet conversions along photoisomerization, photoassociation, and photodissociation reaction paths.

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