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We report the measurement of the photoionization cross sections of the 5S and 5P states of Rb in a two-species Hg and Rb magneto-optical trap (MOT) by the cooling laser for Hg. The photoionization cross sections of Rb in the 5S and 5P states at 253.7~nm are determined to be and , respectively. To measure the 5S and 5P states fractions in the MOT we detected photoionization rate of the 5P state by an additional 401.5~nm laser. The photoionization cross section of Rb in the 5P state at 401.5~nm is determined to be .

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