Shaping the laser control landscape of a hydrogen transfer reaction by vibrational strong coupling. A direct optimal control approach.

Controlling molecular reactivity by shaped laser pulses is a long-standing goal in chemistry. Here, we suggest a direct optimal control approach that combines external pulse optimization with other control parameters arising in the upcoming field of vibro-polaritonic chemistry for enhanced controllability. The direct optimal control approach is characterized by a simultaneous simulation and optimization paradigm, meaning that the equations of motion are discretized and converted into a set of holonomic constraints for a nonlinear optimization problem given by the control functional. Compared with indirect optimal control, this procedure offers great flexibility, such as final time or Hamiltonian parameter optimization. A simultaneous direct optimal control theory will be applied to a model system describing H-atom transfer in a lossy Fabry-Pérot cavity under vibrational strong coupling conditions. Specifically, optimization of the cavity coupling strength and, thus, of the control landscape will be demonstrated.