Quantum exchange coupling: A hypersensitive indicator of weak interactions
Résumé
. The potential energy was calculated for exchange of 2H of OsH3X(PH3)(2)L (X = Cl with L = no ligand and PH3, X = I with L = no ligand) using effective core potential ab initio methods at the MP2 level. The site exchange is found to be energetically easier for Cl than for I, in agreement with experiment. The hydride site exchange in the seven-coordinate species OsH3Cl(PH3)(3) (a model for coordination of either ligand or solvent to Os) is found to be easier than that in the 16-electron species. No dihydrogen ligand is located on the reaction path for site exchange. The current theory which relates quantum exchange to a tunneling effect was used for calculating J(ex) as a function of temperature. The dynamic study was done using several sets of coordinates, in particular the rotation angle phi and the internuclear distance r between the exchanging H. The vibrational levels have been calculated and the symmetry of each level assigned within the permutation group in order to determine the nature of the nuclear spin function associated with each level. It is found that the rotation, phi, gives rise to the largest tunneling effect but that r cannot be neglected. The influence of the temperature, J(ex)(T), was included by a Boltzmann distribution. The results are in qualitative agreement with experiment in that quantum exchange coupling is larger in the case of Cl than in the case of I. Additional ligand L increases the value of the quantum exchange coupling mostly by lowering the activation energy for pairwise exchange.