Interactions of adenine, cytosine, guanine, and thymine with Na+, Mg2+, and Zn2+ cations were studied using an approximate resolution of identity correlated second- order MP2 ( RI- MP2) method with the TZVPP ([ 5s3p2d1f/ 3s2p1d]) basis set. All existing tautomers of adenine, cytosine, and thymine and the eight most stable keto/ enol tautomers of guanine were considered. Cations bind mostly in a bidentate manner, and stabilization energies of these complexes are larger than those in the case when cations bind in a unidentate manner. The cation center dot center dot center dot Y ( Y equal to N or O) distances for divalent metals are shorter than those for Na+ and for Zn2+ are mostly shorter than the Mg2+, Y distance. The intermolecular distances between the cation and the base for complexes containing adenine and cytosine are systematically shorter than those for complexes containing guanine and thymine. Only for cytosine the canonical keto/ amino tautomer structure with ions represents the global minimum. For guanine, the metalated canonical form is again the most stable, but its stabilization energy is within less than 5% of the stabilization energies of the two other rare tautomers, which indicates that the canonical form and these two rare tautomers could coexist. The canonical structures of adenine and thymine in the presence of ions are considerably less stable ( by more than 10%) than the complexes of the rare tautomers. It can be concluded that the interaction of Na+, Mg2+, and Zn2+ cations with cytosine in the gas phase will not induce the change of the canonical form to the rare tautomeric form. In the case of isolated guanine, the equilibrium of the canonical form with rare tautomers can be found. For isolated adenine and thymine the presence of rare tautomers is highly probable.