The three lowest potential energy surfaces, Sigma, Pi, and Pi, of the Van der Waals complex Cl(P-2) + CH4(X-1 A(1)) are derived from accurate ab initio calculations for the vertex, edge and face geometries. The restricted coupled cluster singles, doubles and non-iterative triples excitations [RCCSD(T)] level of theory is applied with a large basis set. The global Van der Waals minimum, which is 348 cm(-1) deep, occurs at R = 3.3 Angstrom on the Sigma surface and is located in the vicinity of the face arrangement. (C) 2002 Elsevier Science B.V. All rights reserved.