An intuitive scheme for controlling the rotational quantum state of a Rydberg molecule is demonstrated experimentally. We determine the accumulated phase difference between the various components of a molecular electron wave packet, and then employ a sequence of phase-locked optical pulses to selectively enhance or depopulate specific rotational states. The angular momentum composition of the resulting wave packet, and the efficiency of the control scheme, is determined by calculating the multipulse response of the time-dependent Rydberg populations. DOI: 10.1103/PhysRevLett.91.243601 PACS numbers: 33.80.Rv Coherent control experiments in molecular systems have tended to employ complex waveforms [1][2][3][4] generated by feedback-controlled learning loops [5]. Despite the fact that they can be remarkably effective even in complex molecules [1][2][3]6] and biological systems [3], they are not intuitive and so it is difficult to unravel the underlying physics [6]. It is extremely tempting to try to control molecular processes from first principles and recognize the control mechanism. Ideal laboratories for the design of logical control schemes are Rydberg wave packets, since the phase parameters are readily determined. The relative phases of the interfering pathways are important since optical control processes rely on the interferences between different excitation pathways. Previous experiments controlling the dynamics of Rydberg electron wave packets have focused on simple atomic systems. Phase-shaped pulses have been employed to excite arbitrary wave packets [7] and to fully characterize their amplitude and phase profile [8][9][10]. Intuitive schemes exploiting trains of phase-locked optical pulses have been employed to create Schrö dinger's cat states [11], to demonstrate Young's double slit interference in an atom [12], to control electronic orbital angular momentum [13], and the radial distribution [14]. In this Letter, we take a step further and develop an intuitive scheme to control the dynamics of a molecular system. We explore the dynamics of a molecular electron wave packet composed predominantly of two Rydberg series belonging to two different rotational quantum states of the molecular ion. We determine the accumulated phase difference and deduce an intuitive pulse sequence to obtain full control over the time-dependent populations of the rotational quantum state of the wave packet.First, consider a wave packet composed of a superposition of two noninteracting Rydberg series, with different orbital angular momenta l and quantum defects l , converging to the same ionization limit. Such a wave packet may be considered as being composed of two separate components and is written r; t nl a nl nl r exp ÿi! nl t , where nl r is the radial wave function of the eigenstate jnli, ! nl ÿ1=2 n ÿ l 2 is its frequency and a nl is its amplitude in the superposition. After an integer number of orbit periods k, each wave packet, corresponding to a channel l, accumulates a phase 2 k l , resulting in an accumulated ph...