Absolute control over the quantum yield of a photodissociation reaction mediated by nonadiabatic couplings.

Control of molecular reaction dynamics with laser pulses has been developed in the last decades. Among the different magnitudes whose control has been actively pursued, the branching ratio between different product channels constitutes the clearest signature of quantum control. In polyatomic molecules, the dynamics in the excited state is quagmired by non-adiabatic couplings, which are not directly affected by the laser, making control over the branching ratio a very demanding challenge. Here we present a control scheme for the CH 3 I photodissociation in the A band, that modifies the quantum yield of the two fragmentation channels of the process. The scheme relies on the optimized preparation of an initial superposition of vibrational states in the ground potential, which further interfere upon the excitation with a broad pump pulse. This interference can suppress any of the channels, regardless of its dominance, and can be achieved over the whole spectral range of the A band. Furthermore, it can be accomplished without strong fields or direct intervention during the dynamics in the excited states: the whole control is predetermined from the outset. The present work thus opens the possibility of extensive and universal control of the channel branching ratio in complex photodissociation processes.