Microhydrated para-dichlorobenzene cation clusters, pDCB(+)-(H2O)(n) with n = 1 and 2, were characterised in the electronic ground state by infrared photodissociation spectroscopy in the O-H and C-H stretch ranges and B3LYP/6-311++G** calculations. The intermolecular pDCB(+)-H2O potential features at least two nonequivalent minima with charge-dipole configuration and comparable binding energies. The pDCB(+)-(H2O)(2) spectrum reveals the presence of two types of isomers, in which either a (H2O)(2) dimer or two single H2O ligands are attached to pDCB(+). The detected pDCB(+) A(H2O)(1,2) complexes are unreactive with respect to nucleophilic substitution. This conclusion is supported for pDCB(+)-H2O by the electronic spectrum of its B X transition. (C) 2009 Elsevier B. V. All rights reserved.