Ab initio based tight-binding Hamiltonian for the dissociation of molecules at surfaces

A tight-binding total-energy (TBTE) method has been developed to interpolate between firstprinciples results describing the dissociation of molecules at surfaces. The TBTE scheme requires only a relatively small number of ab initio energies as input and gives a reliable global representation of the ab initio potential energy surface to within 0.1 eV accuracy compared to the ab initio results. This approach will open the way to the ab initio molecular dynamics description of reactions invoking many atoms and long time scales that are currently not accessible by first-principles methods. [S0031-9007(99)08464-1]