| Classical trajectory and statistical calculations are two commonly used and relatively easily implemented methods for obtaining reaction rates. In this thesis work, both methods are applied to barrierless reactions. Classical trajectories are run on the methyl + diamond radical-radical reaction, and two types of statistical methods are applied to the CO;Physisorption, as well as chemisorption, occurred during trajectory calculations on the methyl + diamond system, and provided some valuable insights into the accuracy of statistical theories for this system. The time at which physisorption changed to chemisorption is used to give an estimate of the time of intramolecular vibrational relaxation (IVR time), a value which is generally difficult to obtain. The probability of chemisorption is used to calculate the reaction rate.;The CO;The chlorobenzene, fluorobenzene, cyanobenzene, and styrene cations were studied at the Hartree-Fock 4-31G, the Hartree-Fock 6-31G*, and the B3LYP/6-31G* (where B3LYP is the Becke, Lee, Yang and Parr three parameter functional) levels of theory. The frequencies for each mode were generally within 5% of each other, and should be considered reliable. The intensities, on the other hand, varied considerably, especially for the larger intensity modes, and should be viewed with caution. |
