Effects of molecular attraction and orientations in the vibration-vibration energy exchange

The effects of molecular attraction and orientations for the energy mismatch variance, vibrational energy level and double-quantum transition, in the vibration-vibration energy exchange, have been considered. The contribution of molecular attraction increases the exchange rate of the purely repulsive interaction, in general, significantly, but which becomes smaller as the temperature is increased. As the energy mismatch is increased, its contribution is also increased, but which is small. However, its contribution for the double-quantum transition is very paramount. At each orientation, the exchange rate constants have been calculated and compared with the results for rotational average, and it is found that the exchange rate is a strong function of the orientation angles of colliding molecules. We have also discussed about the system having the strong interaction such as the hydrogen bond, and it is found that for this system the preferred orientation should be considered in order to calculate the exchange rates. (Author)