A computational modeling of the protonation of corannulene at B3LYP/6-311G(d,p)//B3LYP/6-311G(d,p) and of the binding of lithium cations to corannulene at B3LYP/6-311G(d,p)//B3LYP/6-31G(d,p) has been performed. A proton attaches preferentially to one carbon atom, forming a sigma -complex. The isomer protonated at the innermost (hub) carbon has the best total energy. Protonation at the outermost trim) carbon and at the intermediate (bridgehead rim) carbon is less favorable by ca. 2 and 14 kcal mol(-1), respectively. Hydrogen-bridged isomers are transition states between the sigma -complexes; the corresponding activation energies vary from 10 to 26 kcal mol(-1). With an empirical correction obtained from calculations on benzene, naphthalene, and azulene, the best estimate for the proton affinity of corannulene is 203 kcal mol(-1). The lithium cation positions itself preferentially over a ring. There is a small energetic preference for the 6-ring over the 5-ring binding (up to 2 kcal mol(-1)) and of the convex face over the concave face (3-5 kcal mol(-1)). The Li-bridged complexes are transition states between the pi -face complexes. Movement of the Li+ cation over either face is facile, and the activation energy does not exceed 6 kcal mol(-1) on the convex face and 2.2 kcal mol(-1) on the concave face. In contrast, the transition of Li+ around the corannulene edge involves a high activation barrier (24 kcal mol(-1) with respect to the lowest energy pi -face complex). An easier concave/convex transformation and vice versa is the bowl-to-bowl inversion with an activation energy of 7-12 kcal mol(-1). The computed binding energy of Li+ to corannulene is 44 kcal mol(-1). Calculations of the Li-7 NMR chemical shifts and nuclear independent chemical shifts (NICS) have been performed to analyze the aromaticity of the corannulene rings and its changes upon protonation.