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We investigate experimentally and theoretically the nonlinear properties of two distinct chalcogenide glasses. Nonlinearities are measured through a spatially resolved Mach–Zehnder interferometer. It is shown that the resulting nonlinear index coefficient cannot be correctly described with the usual cubic model. A more convenient theory is developed assuming a medium with two-photon nonlinear absorption and both cubic (
n
2) and quintic (
n
4) nonlinear index variations. The resulting closed-form expression for the effective nonlinear index coefficient allows to extract the cubic and quintic index coefficients.