ΔSCF with Subsystem Density Embedding for Efficient Nonadiabatic Molecular Dynamics in Condensed-Phase Systems

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Accurate simulation of excited-electronic-state dynamics is crucial for understanding chemical processes.
• Conventional Kohn-Sham density functional theory methods are computationally expensive for condensed-phase systems.

Purpose of the Study:

• To present a novel computational approach combining subsystem density embedding with the variational delta self-consistent field method.
• To extend the capabilities for excited-electronic-state calculations.
• To enable efficient simulations of nonadiabatic dynamics in condensed-phase environments.

Main Methods:

• The study employed a combination of subsystem density embedding and the variational delta self-consistent field approach.
• This method was applied to full-atomic nonadiabatic dynamics simulations.
• The system investigated was a solvated diimide.

Main Results:

• The new approach achieved comparable accuracy to conventional Kohn-Sham density functional theory methods for the investigated configuration space.
• The simulation time was significantly shorter compared to the computationally expensive conventional method.
• The method demonstrated its applicability to complex systems like solvated diimide.

Conclusions:

• The presented approach offers a pragmatic and efficient technique for simulating nonadiabatic processes.
• This method is particularly well-suited for applications in the condensed phase, including liquids.
• It extends the toolkit for computational studies of excited-state dynamics.