A theoretical analysis on vibrational-energy transfers in gases

In order to investigate the relationships between three-dimensional and colinear molecular collision models with particular emphasis on the role of repulsive and attractive forces in vibrational energy transfers in gases, a theoretical analysis is developed in this paper. A few known results - mainly the Cottrell and Ream equation, the Takayanagi and the Shin expressions of the transfer probability - relevant to repulsive-forces-dominated processes are obtained and/or discussed in the proposed frame. Light is also given on long-range, attractive-forces-dominated processes. The main result of this investigation is that, when a suitable hypothesis is done on the transfer probability, centrifugal effects on the intermolecular trajectories due to standard potentials are negligible in the low-temperature range. A quasi-colinear collision model, which is found to be correlated to the Cottrell and Ream expression for the transfer probability, is regained from a three-dimensional geometry in these conditions.