Using approximate partition functions and a master equation approach, we investigate the statistical relaxation toward equilibrium in selected CaArn clusters. The Gaussian theory of absorption [J. Chem. Phys., 118, 8739 (2003)] is employed to calculate the average photoabsorption intensity associated with the 4s(2)-->4s(1)4p(1) transition of calcium as a function of time during relaxation. In CaAr6 and CaAr10 simple relaxation is observed with a single time scale. CaAr13 exhibits much slower dynamics, and the relaxation occurs over two distinct time scales. CaAr37 shows even slower relaxation with multiple transients, reminiscent of glassy behavior due to competition between different low-energy structures. We interpret these results in terms of the underlying potential energy surfaces for these clusters. (C) 2003 American Institute of Physics.