Combining Meyer-Miller Hamiltonian with electronic structure methods for on-the-fly nonadiabatic dynamics...

Area of Science:

• Computational Chemistry
• Photochemistry
• Chemical Dynamics

Background:

• Semiclassical methods like Meyer-Miller mapping Hamiltonian with symmetrical quasi-classical windowing (MM/SQC) are crucial for studying nonadiabatic processes.
• Current applications of MM/SQC are often restricted to simplified model Hamiltonians.

Purpose of the Study:

• To implement and validate the MM/SQC method combined with electronic structure calculations for on-the-fly nonadiabatic dynamics simulations.
• To assess the applicability of MM/SQC to realistic molecular systems beyond model Hamiltonians.

Main Methods:

• Integration of the MM/SQC method with OM2/MRCI level electronic structure calculations.
• On-the-fly nonadiabatic dynamics simulations.
• Validation using the photoisomerization process of cis-azobenzene.

Main Results:

• The MM/SQC method successfully reproduced experimental results for the cis-azobenzene photoisomerization.
• The study demonstrated the capability of MM/SQC for simulating dynamics on realistic potential energy surfaces.
• MM/SQC offers a viable alternative to traditional surface hopping simulations.

Conclusions:

• The implemented MM/SQC approach combined with electronic structure calculations is effective for studying nonadiabatic processes in realistic molecular systems.
• MM/SQC provides a valuable alternative to surface hopping methods for photochemical dynamics.
• Optimal windowing procedures for MM/SQC are suggested for future research.