AbstractWe report on a coherent control experiment to selectively excite a well localized nuclear probability density in the electronic ground state of isolated, jet cooled potassium dimer molecules. The basic idea of this control scheme is to take advantage of the motion of a vibrational wave packet created in an intermediate excited electronic state, from which a Franck‐Condon window to the desired final state in the ground state emerges. To realize this concept we apply a resonant stimulated Raman process, in which the two involved laser pulses are separated by a time delay τ1 and their wavelengths are independently tunable. The method enables us to excite ground state vibrational wave packets, whereby the vibrational energy of the wave packet and the position of its generation along the internuclear separation coordinate of the ground state potential energy surface can in principle be freely chosen by the experimentalist. The results we present for the chosen model system K2 strongly support the idea that this control concept might be one possible approach to selectively populate a desired chemical reaction channel in the electronic ground state of a molecule.