Density functional theory is used to study the physico-chemical effects of two metallic thin films separated by distances in a range of 4-10 amperes. In this condition, the electrons from the metallic thin film surfaces tunnel through the energy barrier existing between the separated thin films, creating an electronic distribution in the gap between films. The characteristics and features of this electronic distribution, such as energy, momentum, and number of electrons, can be traced by quantum mechanical analyses. These same features can be tuned by varying metallic thin film properties like thickness, separation between films, and film chemical nature. The possibility to tune the physical properties of the electrons located in the gap between thin films makes the studied systems promising for applications that range from catalysis to nano-electronics. Molecular oxygen, water, and ethylene were located in the gap between thin films in order to study the physical and chemical effects of having those molecules in the gap between thin films. It was observed that the electron structure in the gap modifies the geometric and electronic structure of those molecules placed in the gap. In the case of molecular oxygen, it was found that the dissociation energy can be tuned by changing the separation between thin films and changing the chemical nature of the surface and overlayer of the thin film. For water, it was found that by tuning the chemical nature of the surface and sub-surface of both metallic thin films, molecular water dissociation can occur. When ethylene was located in the gap between Ti/Pt thin films, the molecule converts in an anion radical adopting the geometry and structure of the activated monomer necessary to initiate chain polymerization. Regarding magnetism, it was found that by the surface interaction between Ti/Pt and Pt thin films, the magnetic moment of the system decreases as the separation between thin films decreases. The phenomenon was explained by changes observed in the number of electronic states at the Fermi level and in the exchange splitting as a function of separation between films. Finally, a system that resembles a p-n junction was proposed and analyzed. The system is a junction of two metallic thin films with different electronic density in the gap between surfaces. These junctions can be the building blocks for many electronic devices.