Abstract
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.
Highlights
Laser control of chemical reactions is a challenging field of research
The observed excited state dynamics can be altered using additional pulses tailored to yield outcomes differing from those of the unperturbed dynamics.[14−16] Here, a classification into weak- and strong-field effects is useful, where weak-field pulses induce transitions between states but do not change the shape of the respective potential energy surfaces (PESs) and strong-field pulses influence the dynamics by introducing time-dependent PESs
A desired product state or property is maximized over the course of the complete dynamics, relying on a multitude of runs, resulting in an iteratively adapting pulse.[16,19,27]
Summary
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. According to their electronic character, the pumpUV pulse excites a mixture of MLCT, MSCT, and SC states (Figure 2a). (f) Time evolution of the average S−S bond length for all excited trajectories simulated using the pulse sequences depicted in panels a−e.
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
