Infrared predissociation (IRPD) spectra of Li+(CH4)(1)Ar-n, n = 1-6, clusters are reported in the C-H stretching region from 2800 to 3100 cm(-1). The Li+ electric field perturbs CH4 lifting its tetrahedral symmetry and gives rise to multiple IR active modes. The observed bands arise from the totally symmetric vibrational mode, v(1), and the triple degenerate vibrational mode, v(3). Each band is shifted to lower frequency relative to the unperturbed CH4 values. As the number of argon atoms is increased, the C-H red shift becomes less pronounced until the bands are essentially unchanged from n = 5 to n = 6. For n = 6, additional vibrational features were observed which suggested the presence of an additional conformer. By monitoring different photodissociation loss channels (loss of three Ar or loss of CH4), one conformer was uniquely associated with the CH4 loss channel, with two bands at 2914 and 3017 cm(-1), values nearly identical to the neutral CH4 gas-phase v(1) and v(3) frequencies. With supporting ab initio calculations, the two conformers were identified, both with a first solvent shell size of six. The major conformer had CH4 in the first shell, while the conformer exclusively present in the CH4 loss channel had six argons in the first shell and CH4 in the second shell. This conformer is +11.89 kJ/mol higher in energy than the minimum energy conformer at the MP2/aug-cc-pVDZ level. B3LYP/6-31+G* level vibrational frequencies and MP2/aug-cc-pVDZ level single-point binding energies, D-e (kJ/mol), are reported to support the interpretation of the experimental data.