Electronic action spectroscopy

X-ray dii action spectra of the samples were recorded with a PW 1050 Philips spectrometer with Co Ka incident radiation. Transmission electron micrographs and electron dispersion spectroscopy (EDS) analysis were obtained with a Philips CM 12 instrument equipped with Philips 9100 attachment. 

Divergent views have been expressed on the way in which the tin acts. Its role in limiting the size of platinum ensembles is not in question what is at issue is whether there is any electronic modification of the active centre. It was claimed that, in the reaction of MCP with hydrogen, tin produced positive effects on dehydrogenation and aromatisation that were not shown by either carbon or sulfur they were attributed to an electronic action, for which Mossbauer spectroscopy provided some evidence. In view of the proposal interpretation of the effect of sulfur on butadiene hydrogenation (Section 8.3) it would not be surprising if tin also influenced the platinum ensembles to some degree. 

Visible and UV light sources, which excite electronic transitions, can be used also for PD spectroscopy. By scanning the frequencies of the radiation emitted from the UV/vis light source and measuring PD or electron photodetachment as a function of excitation wavelength, an electronic action spectrum can be constructed in the same way as a vibrational action spectrum is constructed using an IR source. 

Photo-excitation of gas-phase ions may result in the photodetachment of an electron rather than photo-fragmentation. Coulombic considerations dictate that this process is more prevalent for anions than for cations. Electron photodetachment action spectroscopy of trapped anions has proved also to be a valuable source of molecular information. In some systems, electron photodetachment and PD compete. The mechanisms for these two processes in large molecules are yet to be understood fully consequently, their branching ratios in specific experimental conditions cannot be predicted as yet. One exciting possibility is the idea of using frequency and phase-shaped pulses to promote selected photochemical pathways. 

The effect of ionizing radiation on molecular or ionic solids is to eject electrons, which often subsequently react at sites in the material well removed from the residual electron-loss centre. These electron-loss and electron-gain centres, or breakdown products thereof, are paramagnetic and have been extensively studied by e.s.r. spectroscopy. Results for a wide range of organo metals both as pure compounds and as dilute solid solutions are used to illustrate this action. Aspects of the electronic structures of these centres are derived from the spectra and aspects of redox mechanisms are discussed. 

With stringent precautions to avoid the presence of water, polycyclic aromatic hydrocarbons show two one-electron reversible waves on cyclic voltammetry in dimethylformamide (Table 7.1). These are due to sequential one-electron additions to the lowest unoccupied molecular n-orbital [1]. Hydrocarbons with a single benzene ring are reduced at very negative potentials outside the accessible range in this solvent. Radical-anions of polycyclic aromatic hydrocarbons [2] and also alkyl benzenes [3] were first obtained by the action of alkali metals on a solution of the hydrocarbon in tetrahydrofuran. They have been well characterised by esr spectroscopy. The radical-anions form coloured solutions with absorption bands at longer wavelength than the parent hydrocarbon [4,5]. 

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