Ionization Pathway Interference in Photoionization Time Delays in Molecules.

Area of Science:

• Quantum chemistry
• Molecular physics
• Attosecond science

Background:

• Photoionization time-delays offer insights into electron dynamics within molecules.
• Linear conjugated molecules are model systems for studying electron correlation and delocalization.

Purpose of the Study:

• To compute and analyze photoionization time-delays in linear conjugated molecules.
• To elucidate the contributions of different electronic processes to ionization time-delays.

Main Methods:

• Utilized the Wigner scattering approach for theoretical computation.
• Analyzed contributions from interferences between ionization pathways and electron-electron correlations.

Main Results:

• Identified two additive contributions to photoionization time-delays.
• Interference between pathways scales with conjugation length, increasing time-delay.
• Electron correlation contribution is less sensitive to conjugation length.

Conclusions:

• The Wigner scattering approach successfully models photoionization time-delays.
• Interference effects are dominant for longer conjugated systems, explaining experimental observations.
• Understanding these contributions is crucial for controlling and interpreting molecular photoionization.