Due to their extensive present, important and versatile potential applications, metal hydrides (MH) are among the most investigated solid-state systems. Theoretical, numerical and experimental studies have provided a considerable knowledge about their structure and properties, but in spite of that, the basic electronic principles of various interactions present in MH have not yet been completely resolved. Even in the simplest MH, i.e. alkali hydrides (Alk-H), some trends in physical properties, . Int. J. Mod. Phys. B 2010.24:703-710. Downloaded from www.worldscientific.com by ROYAL INSTITUTE OF TECHNOLOGY on 02/02/15. For personal use only. 704 N. Ivanović et al.and especially their deviations, are not well understood. Similar doubts exist for the alkaline-earth hydride (AlkE-H) series, and are even more pronounced for complex systems, like transition metaldoped AlkE-H, alanates and borohydrides. This work is an attempt of explaining some trends in the physical properties of Alk-H and AlkE-H, employing the Bader analysis of the charge distribution topology evaluated by first-principle all-electron calculations. These results are related to some variables commonly used in the explanation of experimental and calculated results, and are also accompanied by simple tight-binding estimations. Such an approach provides a valuable insight in the characteristics of M-H and H-H interactions in these hydrides, and their possible changes along with external parameters, like temperature, pressure, defect or impurity introduction. The knowledge of these basic interactions and processes taking place in simple MH are essential for the design and optimisation of complex MH-systems interesting for practical hydrogen storage applications.