Abstract: The state population distributions of the nascent products for Ca+NF_3→CaF+ NF_2 and Ca+CHF_3→-CaF+CHF_2 reactions were studied by means of LIF in a beam- gas arrangement. From the LIF spectra of CaF and the computer simulations, the CaF vibrational distributions for both reactions were found to be similar to the Boltzmann distribution and the internal energy disposal of CaF was determined quantitatively.The results of the spectral simulation and the information theory computation indicate that NF_2 and CHF_2 radicals were vibrationally and rotationally excited. These two reactions are thought to be direct collision reactions with the “late” exoergicity on potential surface.