Theoretical analysis of the emission spectra of the NaCd excimer

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Abstract
We present simulations of bound–bound and bound–free emissions of the NaCd* excimer, along with new experimental results concerning the red band system. The simulations, based on ab initio potential energy curves, confirm that the initial states are 2 2Σ+ for the red emission and 2 2Π for the blue emission of NaCd*. The two main peaks in the blue band system are due to spin–orbit splitting. The band shape obtained in the simulations is extremely variable, depending on the population distribution of the vibrational states of NaCd*. The comparison of simulated and measured spectra leads us to conclude that, in the experimental conditions adopted here and in previous work, the thermal equilibration of the excimer is far from complete.