Gaussian-based multiconfiguration time-dependent Hartree: A two-layer approach. III. Application to nonadiabatic...

Area of Science:

• Quantum chemistry
• Theoretical chemistry
• Chemical dynamics

Background:

• Nonadiabatic dynamics are crucial for understanding processes like charge transfer.
• Accurate simulation methods are needed for complex molecular systems.
• The Multi-Configuration Time-Dependent Hartree (MCTDH) method is a powerful tool for quantum dynamics.

Purpose of the Study:

• To introduce and apply the Two-Layer Gaussian-based Multi-Configuration Time-Dependent Hartree (2L-GMCTDH) method to nonadiabatic dynamics.
• To assess the performance of different 2L-GMCTDH propagation variants.
• To demonstrate the method's suitability for simulating complex charge transfer dynamics.

Main Methods:

• Application of the 2L-GMCTDH method to a two-state linear vibronic coupling model.
• Simulation of ultrafast, coherent charge transfer dynamics in an oligothiophene-fullerene complex.
• Assessment of single-set, multi-set, and hybrid 2L-GMCTDH propagation variants.
• System dimensions varied from 20 to 100 modes.

Main Results:

• The 2L-GMCTDH method successfully simulates nonadiabatic dynamics.
• Different propagation variants (single-set, multi-set, hybrid) were evaluated.
• The method demonstrates accuracy and efficiency for large system dimensions.
• Coherent charge transfer dynamics were modeled effectively.

Conclusions:

• The 2L-GMCTDH method is a suitable and efficient tool for simulating nonadiabatic dynamics.
• The method can handle complex systems with a large number of degrees of freedom.
• This work paves the way for more sophisticated studies of charge transfer processes.