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When focusing YAG laser pulses at 266nm into a heat-pipe oven containing PbI2 molecules vapor, four red line emissions at 626.0, 619.8, 613.7 and 621.8nm are observed. The photodissociation mechanism of PbI2 molecules and the possible generation channels of these four line emissions are given. Moreover, the dependence of the emission at 626.0nm on incident laser energy and heat-pipe temperature is measured. The experimental observation is well supported by the photodissociation mechanism proposed by us.