Proper construction of ab initio global potential surfaces with accurate long-range interactions

A straightforward linear equation for the reproducing kernel Hilbert space (RKHS) problem is developed, which show that the dependence of dispersion/multipolar coefficients on the short range ab initio data points is completely eliminated and globally accurate potential energy surfaces (PES) are efficiently constructed. This new approach enables an accurate account of the a priori information and the long-range interaction, as demonstrated in the construction of the 1D He-He and 2D Ne-CO PES. A preliminary application of the method to rovibrational data was presented, dealing with the potential curves of the two lowest states of the sodium dimer.