Multi-state multi-mode nuclear dynamics on three isomers of C6H4F2+ using parallelized TDDVR approach

Area of Science:

• Quantum chemistry
• Computational chemistry
• Chemical dynamics

Background:

• Difluorobenzene radical cations exhibit complex electronic dynamics.
• Conical intersections significantly influence excited-state behavior.
• Accurate simulation of these systems is computationally demanding.

Purpose of the Study:

• To investigate the excited-state molecular dynamics of difluorobenzene radical cation isomers.
• To validate a new parallelized Time-Dependent Discrete Variable Representation (TDDVR) methodology.
• To compare TDDVR results with established methods like MCTDH.

Main Methods:

• Development and application of a parallelized Time-Dependent Discrete Variable Representation (TDDVR) method.
• Utilized realistic model Hamiltonians for ortho-, meta-, and para-difluorobenzene radical cations.
• Simulated dynamics involving five electronic states and multiple vibrational modes.

Main Results:

• TDDVR accurately reproduced photoelectron and ionization spectra.
• Population profiles from TDDVR showed good agreement with MCTDH.
• The parallelized TDDVR significantly reduced computation time (over 10x faster).

Conclusions:

• The parallelized TDDVR method is an accurate and efficient approach for simulating complex molecular dynamics.
• This methodology offers a favorable balance between accuracy and computational speed.
• The study provides valuable insights into the excited-state behavior of difluorobenzene radical cations.