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Optical nonlinear refractive properties of a series of Mo(W)/S/Cu planar square dusters are investigated using the Z-scan technique with the ns laser pulses at the wavelength of 532nm.The result shows at the planar metal clusters containing the halogen ligands demonstrate the self-focusing effect,and the other planar metal clusters demonstrate the self-defocusing effect.These facts indicate that the halogen ligands can act as crucial factors in determining the sign of the nonlinear refraction of the Mo(W)/S/Cu planar metal clusters.The analysis of the experimental data shows that the planar clusters with haiogen ligands possess greater refraction volume of the excited state than that of the ground state,while the other planar clusters possess the smaller refraction volume of the excited state than that of the ground state.