SOME APPLICATIONS OF LOCAL DENSITY FUNCTIONAL THEORY TO THE CALCULATION OF REACTION ENERGETICS

We report the results of a local density functional investigation of the energetics of some isomerization reactions, involving the conversions of several unsaturated systems to highly strained molecules related to triprismane and tetrahedrane. The program DMol was used at the DNP level to compute the activation barriers and total energy changes associated with these processes. We also show, for more than 70 first- and second-row atoms and molecules, that the errors (non-local corrections) in their energies correlate very well with the number of electrons, within isonuclear series. This should provide a useful empirical means for improving dissociation energies obtained within the local approximation.