The interrelationships between global reactivity descriptors such as chemical hardness, chemical potential, polarizability and electrophilicity and associated electronic structure principles were investigated in detail by considering distortion along the normal coordinates from the equilibrium structure and internal rotation. The necessary conditions on the extremum of electrophilicity were probed along with other electronic structure principles associated with the global reactivity descriptors. It was observed that an extremum in electrophilicity is obtained where both chemical potential and chemical hardness attain their respective exiremal values in course of the molecular vibrations as well as internal rotations.