An investigation of the excited-state dynamics Of SO2(H2O)(n) (n = 1-5) clusters following excitation by ultrafast laser pulses to 4.7 eV (coupled (1)A(2) and B-1(1) states) and 9.3 eV (F band) is presented. The findings for the coupled (1)A(2) and B-1(1) states are in good agreement with published computational work(7) and indicate the division of the initial excited-state population into the double well produced by the coupled states. A photoinduced ion-pair formation process is proposed as a likely source of the observed dynamic behavior following the 9.3 eV excitation. Energetics calculations are also presented that support the ion-pair mechanism. A lack of cluster size dependence in the measured time constants indicate surface solvation Of SO2 rather than a cluster structure with the SO2 molecule fully encompassed by water molecules.