The vibrational motion of molecules represents a fundamental example of an anharmonic oscillator. Using a prototype molecular system, HeH^{+}, we demonstrate that appropriate laser pulses make it possible to drive the nuclear motion in the anharmonic potential of the electronic ground state, increasing its energy above the potential barrier and facilitating dissociation by purely vibrational excitation. We find excellent agreement between the frequency-dependent response of the helium hydride molecular cation to both classical and quantum mechanical simulations, thus removing any ambiguities through electronic excitation. Our results provide access to the rich dynamics of anharmonic quantum oscillator systems and pave the way to state-selective control schemes in ground-state chemistry by the adequate choice of the laser parameters.