Outer-Valence Intermolecular Coulombic Decay and Fragmentation Dynamics of p-Xylene•••Trimethylamine Complex

Area of Science:

• Physical Chemistry
• Chemical Physics
• Molecular Dynamics

Background:

• Intermolecular Coulombic Decay (ICD) is a key process in molecular clusters.
• Understanding cluster fragmentation dynamics is crucial for chemical analysis.

Purpose of the Study:

• To investigate the ICD mechanism in p-xylene•trimethylamine (PX•TMA) clusters.
• To analyze the fragmentation dynamics and translational energy of the TMA cation.
• To explore the potential of ICD for differentiating binary complex structures.

Main Methods:

• Resonant two-color two-photon excitation.
• Velocity-mapped imaging.
• Born-Oppenheimer molecular dynamics (BOMD) simulations.

Main Results:

• ICD of the PX•TMA cluster leads to TMA cation formation.
• The translational energy distribution of the TMA cation is linked to the initial {Ar}C-H•••N hydrogen-bonded structure.
• The translational energy profile can distinguish between different binary complex structures.

Conclusions:

• The study elucidates the ICD mechanism in PX•TMA clusters.
• Initial hydrogen bonding significantly influences fragmentation dynamics.
• ICD-derived translational energy profiles offer a method for structural characterization of molecular complexes.