Molecules interfacing electrodes with

Valuable information can be obtained from thermal desorption spectra (TDS) spectra, despite the fact that electrochemists are somewhat cautious about the relevance of ultrahigh vacuum data to the solution situation, and the solid/liquid interface in particular. Their objections arise from the fact that properties of the double layer depend on the interaction of the electrode with ions in the solution. Experiments in which the electrode, after having been in contact with the solution, is evacuated and further investigated under high vacuum conditions, can hardly reflect the real situation at the metal/solution interface. However, the TDS spectra can provide valuable information about the energy of water adsorption on metals and its dependence on the surface structure. At low temperatures of 100 to 200 K, frozen molecules of water are fixed at the metal. This case is quite different from the adsorption at the electrode/solution interface, which usually involves a dynamic equilibrium with molecules in the bulk. 

The contribution of the metal to the double layer was discussed in Sections 6.6.7 to 6.6.9. However, we have said little about the ions in solution adsorbed on the electrode and how they affect the properties of the double layer. For example, when presenting the Stem model of the double layer (Section 6.6.6), we talked about ions sticking to the electrode. How does an interface look with ions stuck on the metal What is the distance of closest approach Are hydrated ions held on a hydrated electrode i.e., is an electrode covered with a sheet of water molecules Or are ions stripped of their solvent sheaths and in intimate contact with a bare electrode What are the forces that influence the sticking of ions to electrodes ... 

Adhesion — (a) When two compact materials, be they solid or liquid, are in intimate contact, attractive forces may act between their surface atoms or molecules. These forces are typically - van der Waals forces and electrostatic forces. The work of adhesion W (b)b(a) between the two phases (denoted A and B) is WAB = yA+yB -yAB> where yA and yg are the - interfacial tensions of A and B when each is interfaced only with the vapor phase, and yAB is the interfacial tension of the interface between A and B. In a more rigorous treatment (at thermodynamic equilibrium) each phase is regarded as saturated with the other phase [i]. In the case of liquid phases the equation for the work of adhesion is referred to as the -> Dupre equation. Adhesion forces between particles, or between particles and surfaces, dominate gravity for small particle sizes (pm and sub-pm range). In electrochemistry, increasing attention is being given to various phenomena related to the adhesion of vesicles [ii], particles [iii], droplets [iv], cells [v], etc. to electrode surfaces. 

The interaction of CO with the solid surface produces several physical and chemical effects on the vibrational properties of the adsorbed species. The adsorption of CO can be envisaged as a two-dimensional condensation, leading to lateral coupling between adsorbed molecules. The vibrational properties of adsorbed CO can thus be used to monitor the effects of other interface properties, such as surface defects, two-dimensional phase transitions [45] and co-adsorption. Finally, CO is formed as an intermediate or poison during the oxidation of several organic molecules at electrodes, thus constituting one of the subjects of interest in electrocatalysis. 

To date, a relatively small number of materials have been explored in a molecular spintronics device and much remains to be understood. For example, the couphng between the molecular layer and the magnetic electrodes is believed to play a very significant role due to the discrete nature of the molecule s HOMO and LUMO, in contrast to the band properties inherent in a continuous-lattice material. The energies of the frontier orbitals with respect to the Fermi level of the electrodes, the broadening of the frontier orbitals into (narrow) bands and the orientation-dependent orbital overlap between molecule and electrode will all contribute to the transport of spins across the interface. Study of the magnetic properties of molecule surface systems is, therefore, highly important and may also lead to new types of spintronic devices. 

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