Calculation of vibrational and rotational energy transfer between HF, DF, HCl, and CO2

Publisher Website
Google Scholar
Abstract
A theory of vibrational energy transfer which retains the exponential form of the scattering operator is applied to energy transfer between vibrationally excited HF, DF, HCl, and CO2. The calculations contain several new features, including use of curved classical trajectories and vibrational wavefunctions obtained numerically from an RKR potential. Cross sections for multiquantum pure rotational changes caused by the dipole-quadrupole interaction are calculated. These multiquantum rotational transitions play an important role in vibrational energy exchange by allowing large vibrational energy defects to be absorbed by the rotational degrees of freedom. Agreement between theory and experiment is excellent. Cross sections calculated for simultaneous transfer of two vibrational quanta from HF or HCl to CO2 are very small. However, for DF–CO2 the calculated two-quantum-transfer cross section is only a factor of 2–6 smaller than that for single-quantum transfer.