Vibrational Transitions and the Intermolecular Potential

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Abstract
Temperature‐dependence studies of vibrational collision lifetimes by the authors have indicated that the application of the Schwartz, Slawsky, and Herzfeld theory to substituted methane molecules with heavy surface atoms results in repulsive ranges which are shorter than those expected from a Lennard‐Jones 6:12‐type interaction. We have shown that the 28:7 potential suggested by Hamann and Lambert for quasi‐spherical molecules gives ranges which are in better agreement with experiment. Also, experimental relaxation times of CHClF2‐argon and CHClF2‐helium mixtures have been used to obtain the collision lifetimes for the CHClF2 molecule undergoing either argon or helium collisions. The results can be explained using the SSH theory, if the 6:12 ranges for helium and argon are averaged with the shorter experimental range for CHClF2.

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