Modeling the Evolution of Laser-Induced Electronic Coherences with Trajectory Surface Hopping

Area of Science:

• Computational Chemistry
• Quantum Dynamics
• Molecular Physics

Background:

• Ultrafast laser pulses create coherent superposition of electronic states in molecules.
• Modeling this requires accounting for coupled electron-nuclear motion and decoherence.
• Conical intersections play a key role in molecular dynamics.

Purpose of the Study:

• Introduce Trajectory Surface Hopping with Projected Forces and Momenta (TSH-PFM).
• Provide a numerically inexpensive method for simulating molecular dynamics.
• Describe dynamics initiated by coherent electronic states.

Main Methods:

• Developed the Trajectory Surface Hopping with Projected Forces and Momenta (TSH-PFM) method.
• Applied TSH-PFM to BMA[5,5], para-xylene, and fulvene molecules in full dimensionality.
• Validated TSH-PFM against existing quantum mechanical results.

Main Results:

• TSH-PFM accurately reproduces quantum mechanical results for benchmark molecules.
• Demonstrated the method's efficiency for simulating complex molecular dynamics.
• Observed significant impact of initial electronic coherences on charge distribution in glycine.

Conclusions:

• TSH-PFM is a computationally efficient and accurate method for simulating molecular dynamics.
• The method is well-suited for studying systems with initial coherent electronic states.
• Initial electronic coherences significantly influence early-stage molecular charge distribution.