Taming Disulfide Bonds with Laser Fields. Nonadiabatic Surface-Hopping Simulations in a Ruthenium Complex

Laser control of chemical reactions is a challenging field of research. In particular, the theoretical description of coupled electronic and nuclear motion in the presence of laser fields is not a trivial task and simulations are mostly restricted to small systems or molecules treated within reduced dimensionality. Here, we demonstrate how the excited state dynamics of [Ru(^S-Sbpy)(bpy)₂]²⁺ can be controlled using explicit laser fields in the context of fewest-switches surface hopping. In particular, the transient properties along the excited state dynamics leading to population of the T₁ minimum energy structure are exploited to define simple laser fields capable of slowing and even completely stopping the onset of S-S bond dissociation. The use of a linear vibronic coupling model to parametrize the potential energy surfaces showcases the strength of the surface-hopping methodology to study systems including explicit laser fields using many nuclear degrees of freedom and a large amount of close-lying electronic excited states.