The present work focuses on the influence of aromatic stacking on the ability of an aromatic nitrogen base to accept a hydrogen bond. Substituent effects were studied at the MP2 level for 10 complexes of a substituted benzene stacked with pyridine in a parallel offset conformation. The interaction energies between each substituted benzene and pyridine were analyzed in terms of Hartree-Fock, correlation, and electrostatic contributions. It appears that the basicity of pyridine is directly related to the electrostatic interaction between the cycles. It increases with increasing electron donating character of the benzene substituents. Also, density functional theory based descriptors such as global and local hardnesses and the benzene ring polarizability are found to adequately predict the interaction energy. These findings may be important in the study of DNA/ RNA chains.