Vibrationally Resolved B 1s Photoionization Cross Section of BF3

Area of Science:

• Atomic and Molecular Physics
• Chemical Physics
• Surface Science

Background:

• Photoelectron diffraction is a powerful technique for solid-state structural analysis.
• Gas-phase studies using this method face challenges due to low signal intensity.
• Boron trifluoride (BF3) serves as a model system for gas-phase photoelectron diffraction studies.

Purpose of the Study:

• To investigate the vibrationally resolved B 1s photoionization cross section of the BF3 molecule.
• To explore the phenomenon of photoelectron diffraction in a gas-phase molecular system.
• To determine structural information for both the neutral ground state and the core-ionized cation of BF3.

Main Methods:

• High-resolution photoelectron spectroscopy measurements.
• State-of-the-art static-exchange calculations.
• Time-dependent Density Functional Theory (DFT) calculations.

Main Results:

• Observed evolution of the cross section's photon energy dependence from photoelectron wave trapping to diffraction oscillations.
• Successfully accessed structural information for both neutral and core-ionized BF3.
• Investigated eight relative vibrationally resolved photoionization cross sections due to significant geometry change upon ionization.

Conclusions:

• Photoelectron diffraction is applicable to gas-phase molecules like BF3 for structural determination.
• The study provides detailed insights into molecular structure and dynamics of BF3 and its core-ionized state.
• Recoil effects in photoelectron emission were also discussed, adding to the comprehensive analysis.