Combining dissociative ionization pump-probe spectroscopy and ab initio calculations to interpret dynamics and control through conical intersections.

Nonadiabatic processes play an important role in molecular dynamics, and understanding these processes better can help interpret and guide control over molecules. We are using high level electronic structure calculations in combination with intense, shaped, ultrafast laser pulses to study excited state dynamics in the nucleic acid bases, cytosine and uracil. These molecules have very short excited state lifetimes as they relax radiationless through conical intersections after absorption of UV radiation. The presence of more than one relaxation pathway provides the possibility to control which pathway can be involved in the dynamics. In our approach the molecules were excited using ultrafast laser pulses in the deep UV and then probed with strong field near infrared pulses which ionize and dissociate the molecules. Key to this approach is the fact that different fragments exhibit different dynamics and we can correlate these fragments, and their associated dynamics, to the various pathways involved in the neutral dynamics. Multiconfigurational electronic structure methods were used to calculate potential energy surfaces of the neutral and ionic states involved in the dynamics. Calculating mechanisms for fragmentation in the ion enables us to relate specific fragments to different neutral pathways, and use them as signatures to follow the dynamics. Possibilities for control are also discussed.