Ab Initio Polariton Transport Dynamics with the Classical Path Approximation

Area of Science:

• Quantum dynamics
• Materials science
• Computational chemistry

Background:

• Simulating polariton transport requires computationally expensive quantum dynamics of many electronic degrees of freedom.
• Fully ab initio dynamics simulations are often intractable due to high computational cost.

Purpose of the Study:

• To present a novel ab initio framework for simulating polariton transport dynamics.
• To establish the classical path approximation (CPA) as an efficient method for polaritonics.

Main Methods:

• Utilized the classical path approximation (CPA) to remove the need for excited-state nuclear gradients.
• Developed an ab initio framework for polariton transport dynamics simulations.
• Performed benchmark comparisons with full excited-state force evaluations.

Main Results:

• Demonstrated CPA's suitability for polaritonic systems due to vanishing excited-state forces from light-matter coupling.
• Achieved excellent agreement between CPA and full calculations for polariton group velocities and mean-squared displacements.
• Reproduced experimental trends in BODIPY molecules using ab initio CPA simulations.

Conclusions:

• The classical path approximation (CPA) is a computationally efficient tool for ab initio simulations of polariton transport.
• CPA accurately captures key physical trends in hybrid light-matter systems.
• This framework facilitates investigations of transport and energy flow in polaritonic systems.