Combining Optical Control and Geometrical Optimization for Efficient Control of Competing Molecular Photoinduced...

Area of Science:

• Quantum Chemistry
• Photochemistry
• Molecular Dynamics

Background:

• Maximizing photochemical process yields is crucial for controlling chemical reactions.
• Optimization strategies include tuning driving fields (optical control) and initial wave functions (geometrical optimization).

Purpose of the Study:

• To combine optical control and geometrical optimization algorithms in an iterative process.
• To investigate the enhancement of population transfer to the second excited state of the molecular hydrogen cation.

Main Methods:

• Iterative optimization combining driving field and initial wave function adjustments.
• Application to a pump-pump scheme for population transfer in molecular hydrogen cation.

Main Results:

• Demonstrated very fast convergence and significant yield improvement.
• Revealed the critical role of initial vibrational coherences in photoinduced processes.
• Showcased how maximizing total electronic vs. bound population leads to distinct initial wave function dynamics.

Conclusions:

• The combined optimization strategy offers a powerful method for enhancing photochemical yields.
• Initial wave function characteristics, particularly vibrational coherences, profoundly influence photoinduced dynamics.
• Control over population dynamics can be achieved by tailoring initial states for specific outcomes (dissociation vs. bound states).