Optimal control of mode-selective femtochemistry in multidimensional systems

We present a strategy for optimal control of the ground-state dynamics in multidimensional systems based on a combination of the semiclassical Wigner distribution approach with direct quantum chemical molecular dynamics (MD) "on the fly." This allows one to treat all degrees of freedom without the need for precalculation of global potential energy surfaces. We demonstrate the scope of our theoretical procedure on two prototype systems representing rigid symmetrical molecules (Na3F) and flexible biomolecules with low-frequency modes (glycine). We show that the ground-state isomerization process can be selectively driven by ultrashort laser pulses with different shapes which are characteristic of the prototype systems. Thus, our method opens perspectives for control of the functionality of biomolecules. Moreover, assignment of the underlying processes to pulse shapes based on MD allows one to use optimal control as a tool for analysis.