Control of bond-selective photochemistry in CH BrCl using adaptive femtosecond pulse shaping

Abstract:

Adaptive femtosecond laser pulse shaping is employed to achieve bond selective photodissociation/photoionization of CH₂ClBr in the gas phase. The photoproduct signal measured in a reflectron time-of-flight mass spectrometer is used as feedback to improve iteratively the spectral phases of the laser pulse via an evolutionary algorithm. We observe an increase of the fission of the stronger versus the weaker carbon halogen bond by 100%. Single parameter control schemes proved unable to achieve bond-selectivity. The complexity of the control problem is addressed by mapping it onto the well-known problem of maximizing second-harmonic generation (SHG). Further spectroscopic results indicate that the control involves manipulation of wave-packet dynamics on the neutral surfaces.