The newly developed methodology presented in this work combines theoretical structure predictions with electric beam deflection measurements in order to discriminate the geometric structure of small inorganic clusters in the gas phase. For this purpose the deflection of the particles in an inhomogeneous electric field is studied. The observed deflection is directly connected to the Stark effect and consequently to the polarizability and permanent electric dipole moment of the small aggregates. Hence, a quantum chemical prediction of the experimentally measured observables can be used to simulate the molecular beam deflection profiles for different cluster isomers. The theoretical description of the beam deflection behavior is achieved by predicting the lowest lying cluster isomers, employing density functional theory calculations combined with an evolutionary inspired genetic algorithm. In a next step the rotational dynamics for each isomer in the electric field is simulated. By comparing the simulated and experimentally measured beam deflection profiles a discrimination of the different cluster isomers is possible and hence the geometrical structure of the cluster in the molecular beam can be deduced. The described methodology and its applications are highlighted for Ge, Au-Ag, Si, Sn-Bi and Sn-Pb clusters. In particular, the influence of the cluster size and composition on the geometric structure of these clusters is analyzed in detail and structural trends are deduced when possible. Additionally, present experimental as well as theoretical limitations of this method are discussed and hence future improvements of the methodology are outlined.