Vibrational energy transfer studies in CO2–hydrocarbon mixtures

Rate constants for the transfer of energy from CO2(00°1) to ethane and n-butane were measured using the laser induced fluorescence technique. The large magnitudes and the negative temperature dependence of the energy transfer rates indicate that near-resonant energy transfer processes caused by long range forces are responsible for the deactivation of the asymmetric stretching mode of CO2. It is shown that the combination bands in the alkanes are likely to receive the energy from CO2(00°1). Using Sharma–Brau theory with Tam’s modification and our experimental results, the square of the transition dipole matrix elements of ν3+ν6 and ν9+ν11 bands of ethane are estimated. At any given temperature in the range 300–730 °K, the energy transfer cross section was found to increase linearly with n of CnH2n+2. It is suggested that the absorption intensity of the combination bands of the alkanes also increases linearly with n in the spectral range 2300–2400 cm−1.