Mapping of Wave Packet Dynamics at Conical Intersections by Time- and Frequency-Resolved Fluorescence Spectroscopy: A...

Area of Science:

• Quantum dynamics
• Spectroscopy
• Chemical physics

Background:

• Conical intersections are crucial in photochemistry and molecular dynamics.
• Understanding wave packet dynamics at these intersections is key to controlling chemical reactions.
• Dissipative environments significantly influence molecular processes.

Purpose of the Study:

• To theoretically investigate the monitoring of wave packet dynamics at conical intersections.
• To explore the impact of dissipative environments on these dynamics.
• To assess the utility of time- and frequency-resolved fluorescence spectroscopy for characterization.

Main Methods:

• Utilized a three-state two-mode model of a conical intersection.
• Employed the hierarchy equations-of-motion method for quantum dynamics in dissipative systems.
• Applied the equation-of-motion phase-matching approach for spectroscopic signal calculation.

Main Results:

• Accurately and efficiently simulated ideal and measurable time- and frequency-gated fluorescence spectra.
• Demonstrated that these spectra reveal key aspects of wave packet dynamics.
• Showcased the influence of environment-induced dissipation on spectral features.

Conclusions:

• Time- and frequency-resolved fluorescence spectra are powerful tools for studying conical intersection dynamics.
• These spectroscopic methods can elucidate the effects of environmental dissipation.
• Femtosecond time-resolved fluorescence up-conversion spectroscopy is effective for characterizing ultrafast dynamics.