Vibrational energy transfer processes in dideuteromethane were studied using a variety of complementary, laser induced fluorescence techniques. The time evolution of population in all infrared active fundamentals, except ν4 and ν7, were monitored following three different initial conditions: excess population in ν7, excess population in a 2000 cm-1 state, and simultaneous excess population in ν4 and a 2000 cm-1 state. These initial perturbations were achieved by irradiating the molecule with the R(22), P(24), and P(38) lines of the 9.6μ CO2 laser band. Experiments were performed on pure CH2D2, CH2D2 rare gas, and CH 2D2-O2 mixtures in order to elucidate the vibrational equilibration pathways in the parent molecule. The experimental studies afforded a complete map of the energy transfer pathways between the fundamentals and yielded rate constant for some specific V-V steps. The validity of these conclusions were confirmed by numerical modeling of the system. Theoretical calculations based on the Sharma and Brau, and Schwartz, Slawsky, and Herzfeld formulations were performed to conclude that V-V processes in CH2D2 are governed almost exclusively by hard core collisions.
|Original language||English (US)|
|Number of pages||19|
|Journal||The Journal of Chemical Physics|
|State||Published - Dec 1 1980|
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry