Fully quantum study of vibrational energy transfer between H2and D2

摘要

We present here the results of a detailed study of the collisional transfer of vibrational energy between H2and D2. Following our work on D2sngbnd;D2collisions J. Chem. Phys.59, 6254 (1973), we carry out a fully quantum treatment of the collision dynamics, assuming a collinear geometry. We have used one fullyab initioand four different model interaction potentials. For both the 10rarr;01 and 11rarr;02 processes, we find that the transition probabilities are extremely sensitive to the choice of potential surface. Another result is that nearesthyphen;atom model potentials yield inelastic probabilities which are too large. We further show that longhyphen;range forces play a far less important role in the case of these offhyphen;resonant processes than for the D2sngbnd;D2nearhyphen;resonant collisions. Also of interest is the result that the calculatedVsngbnd;Vtransition probabilities are largely insensitive to the choice of a harmonic or Morse oscillator description of the colliding molecules.