Non-equilibrium (NEMD) and equilibrium (EMD) molecular dynamics simulations are performed to investigate the vibrational cooling and asymmetric stretch spectral evolution of highly excited carbon dioxide produced in the photodissociation of organic peroxides in the solvents dichloromethane, carbon tetrachloride and xenon. Due to strong Fermi resonance the symmetric stretching and bending modes of carbon dioxide in CH2Cl2 and CCl4 jointly relax on a ten and hundred picosecond timescale, respectively, which is in accordance with experiment. However, the high frequency CO2 asymmetric stretch vibration relaxes on a considerably longer time scale because of weak interaction with the other modes. The relaxation rate coefficients of (and works done by) different modes obtained from NEMD and the Landau-Teller rate coefficients calculated through equilibrium force time correlation functions are in reasonable agreement. The analysis of these results leads to the conclusion that, in contrast to xenon where the relaxation takes about 20 ns, the shorter time scales in CH2Cl2 and CCl4 are caused by efficient near resonant vibration to vibration energy transfer from carbon dioxide to solvent molecules. The results of the non-equilibrium simulations are used to monitor the quasi-stationary asymmetric stretch infrared spectra of carbon dioxide during the cooling process. Comparison of the corresponding experimental results suggests that carbon dioxide initially is produced with a broad distribution of energy disposed in its bend and symmetric stretch modes while the asymmetric stretch mode remains unexcited.