Accurate ground state potential of Cu2 up to the dissociation limit by perturbation assisted double-resonant four-wave mixing

Perturbation facilitated double-resonant four-wave mixing is applied to access high-lying vibrational levels of the X1 Sigma g+(0g+) ground state of Cu-2. Rotationally resolved transitions up to v '' = 102 are measured. The highest observed level is at 98% of the dissociation energy. The range and accuracy of previous measurements are significantly extended. By applying the near dissociation equation developed by Le Roy [R. J. Le Roy, J. Quant. Spectrosc. Radiat. Transfer 186, 197 (2017)], a dissociation energy of D-e = 16 270(7) hc cm(-1) is determined, and an accurate potential energy function for the X1 Sigma g+(0g+) ground state is obtained. Molecular constants are determined from the measured transitions and by solving the radial Schrodinger equation using this function and are compared with results from earlier measurements. In addition, benchmark multi-reference configuration interaction computations are performed using the Douglas-Kroll-Hess Hamiltonian and the appropriate basis of augmented valence quadruple zeta type. Coupled-cluster single, double, and perturbative triple calculations were performed for comparison.