Tracking excited state dynamics with coherent control: automated limiting of population transfer in LDS750

Closed loop automated pulse shaping experiments are conducted to investigate population transfer in solutions of the laser dye LDS750 in acetonitrile and ethanol. Guided by a genetic algorithm, the optical phases of broadband noncollinear parametric amplifier pulses are modulated by a micromachined deformable mirror to minimize sample fluorescence. The objectives were to test if nonlinearly chirped pulses could reduce population transfer below levels attained by their linearly chirped analogues, and if so, whether the resulting pulse shapes could be rationalized in terms of the photoinduced molecular dynamics. We further aimed to discover how the optimal solutions depend on the pulse fluence, and on the nature of the solvent. Using frequency resolved optical gating, the optimal field is shown to consist of a transform limited blue portion, which promotes population to the excited state, and a negatively chirped red tail, which follows the Stokes shifting of the excited density and dumps it back down to the ground state through stimulated emission. This is verified by comparing the optimal group delay dispersion with multichannel transient absorption data collected in acetonitrile. The optimal pulse shape was not significantly affected by variation of pulse fluence or by the change of solvent for the two polar liquids investigated. These results are discussed in terms of accumulated insights concerning the photophysics of LDS750 and the capabilities of our learning feedback scheme for quantum control.