Time-resolved photoion and photoelectron velocity mapped images from NO(2) excited close to its first dissociation limit [to NO(X(2)Pi) + O((3)P(2))] have been recorded in a two colour pump-probe experiment, using the frequency-doubled and frequency-tripled output of a regeneratively amplified titanium-sapphire laser. At least three processes are responsible for the observed transient signals; a negative pump-probe signal (corresponding to a 266 nm pump), a very short-lived transient close to the cross-correlation of the pump and probe pulses but on the 400 nm pump side, and a longer-lived positive pump-probe signal that exhibits a signature of wavepacket motion (oscillations). These transients have two main origins; multiphoton excitation of the Rydberg states of NO(2) by both 266 and 400 nm light, and electronic relaxation in the 1(2)B(2) state of NO(2), which leads to a quasi-dissociated NO(2) high in the 1(2)A(1) electronic ground state and just below the dissociation threshold. The wavepacket motion that we observe is ascribed to states exhibiting free rotation of the O atom about the NO moiety. These states, which are common for loosely bound systems such as a van der Waals complex but unusual for a chemically-bound molecule, have previously been observed in the frequency domain by optical double resonance spectroscopy but never before in the time domain.

We demonstrate experimentally that several classes of phase functions are capable of enhancing the amount of three-photon fluorescence from molecular iodine by at least a factor 3 with respect to an unshaped pulse. The investigated functions include third-order Taylor expansions, π-steps and highly structured forms identified by an evolution strategy. The mechanism of the observed control is investigated using wavepacket simulations and found to be due to a time-delay in the second resonance of the excitation ladder.

A representation of the search space in optical pulse shaping problems employing an acousto-optic programmable dispersive filter (AOPDF) is presented for use in closed-loop learning experiments where the optimal spectral phase function to some control problem is determined by an iterative learning algorithm. The representation allows the algorithm to select a value for the optical chirp at each frequency control point such that only acoustic grating functions which preserve the spectrum of the shaped pulses are tested. The limits of this space with respect to the rate of applied optical chirp, optical bandwidth and acoustic power are examined and tested through diffraction efficiency studies performed using a commercial AOPDF. The main benefits of this representation are the elimination of undesirable frequency mixing effects, reduction of diffraction efficiency variation between arbitrary pulse shapes and faster convergence of the evolutionary algorithm.

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