In a two-color femtosecond pump-probe experiment photoelectron spectra were detected to map the nuclear wave packet in the 2(1)Sigma(u)(+) Na-2 double-minimum state. The wave packet serves as a local probe for the R-dependent ionization probability. The pump photon energy of 3.65 eV allows to access a range of internuclear distances from 3 to 9Angstrom. The bound 1(2)Sigma(g)(+) and the repulsive 1(2)Sigma(u)(+) ionic states are accessible with the probe photon energy of 4.68 eV. Energy-resolved photoelectron measurements permitted to rule out competing ionization pathways. Our results show that for the bound ionic state the ionization probability at the outer turning point is 4.0+/-0.4 times larger than that at the inner turning point. (C) 2003 Elsevier B.V. All rights reserved.