Extension of the composite CBS-QB3 method to singlet diradical calculations

Research paper by Baptiste Sirjean, René Fournet, Pierre-Alexandre Glaude, M. F. Ruiz-Lopez

Indexed on: 14 Jun '07Published on: 14 Jun '07Published in: Physics - Chemical Physics


The composite CBS-QB3 method is widely used to obtain accurate energies of molecules and radicals although its use in the case of singlet diradicals gives rise to some difficulties. The problem is related to the parameterized correction this method introduces to account for spin-contamination. We report a new term specifically designed to describe singlet diradicals separated by at least one CH2 unit. As a test case, we have computed the formation enthalpy of a series of diradicals that includes hydrocarbons as well as systems involving heteroatoms (nitrogen, oxygen). The resulting CBS-QB3 energies are very close to experiment.