Time-dependent density functional theory study on direction-dependent electron and hole transfer processes in...

Area of Science:

• Physical Chemistry
• Materials Science
• Computational Chemistry

Background:

• Electron and hole transfer are fundamental processes in molecular systems.
• Understanding charge transport dynamics is crucial for developing new materials and technologies.
• Sulfur allotropes, particularly α-sulfur, present unique electronic and structural properties.

Purpose of the Study:

• To investigate direction-dependent electron and hole transfer processes in α-sulfur using real-time time-dependent density functional theory (TD-DFT).
• To elucidate the interplay between charge transfer and nuclear motion in molecular systems.
• To explore the stability of resulting molecular structures after charge transfer events.

Main Methods:

• Real-time time-dependent density functional theory (TD-DFT) calculations.
• Modeling of electron and hole transfer in α-sulfur (S₈) molecular systems.
• Analysis of coupling between electronic and nuclear (vibrational) motion.

Main Results:

• Electron transfer from a charged S₈ molecule to a neutral monomer occurs on a timescale comparable to strong infrared-active molecular vibrations.
• Strong electron-nucleus coupling leads to the opening of the S₈ ring before electron transfer completion, forming a stable open-ring structure.
• Hole transfer exhibits a weak infrared-active peak, indicating minimal nuclear scattering and no significant structural changes.

Conclusions:

• The study reveals a strong electron-phonon coupling mechanism in α-sulfur that influences charge transfer dynamics and molecular stability.
• The findings highlight the importance of considering nuclear motion in charge transfer processes within molecular systems.
• The presented computational approach offers valuable insights for the field of charge transport in molecular systems, particularly for sulfur-based materials.