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A quantum-mechanical framework for calculating the photoabsorption cross section of atomic clusters, which explicitly includes the thermal motion of the ions, is proposed. We compute the photoabsorption cross section of Na 8 for ionic temperatures below and above melting. At equilibrium, the line shape of Na 8 is dominated by two peaks separated by 200 meV. This structure is found to survive up to T 100 K. With increasing temperatures, the cross section undergoes a shape phase transition suchdoi:10.1103/physrevlett.79.4986 fatcat:b4rs2biadzfetbktoqpb455m24