Electron attachment to microhydrated 4-nitro- and 4-bromo-thiophenol

Area of Science:

• Physical Chemistry
• Chemical Physics
• Molecular Dynamics

Background:

• Electron attachment to molecules is fundamental to understanding chemical reactions.
• Thiophenols with functional groups exhibit unique electron interaction properties.
• Microhydration's influence on electron-induced reactions is an active area of research.

Purpose of the Study:

• Investigate microhydration effects on electron attachment to para-substituted thiophenols (bromothiophenol and nitro-thiophenol).
• Analyze anion formation pathways and fragmentation dynamics.
• Correlate experimental findings with theoretical calculations.

Main Methods:

• Low-energy electron attachment experiments (< 8 eV) on heterogeneous clusters of thiophenols with water.
• Ab initio calculations for reaction energetics.
• Computational modeling of simplified bromothiophenol-water systems.

Main Results:

• Nitro-thiophenol primarily undergoes associative electron attachment, unaffected by microhydration.
• Bromothiophenol fragments significantly, producing Br- and (BTP-H)- anions.
• Microhydration suppresses fragmentation for both, but Br- channel remains intense in bromothiophenol, forming hydrated clusters; anion dissociation dynamics depend on hydration site.

Conclusions:

• Microhydration significantly alters electron attachment pathways in bromothiophenol, favoring hydrated fragment anions.
• The observed differences in dissociation dynamics between nitro-thiophenol and bromothiophenol are linked to their electronic structures and functional groups.
• Anion formation and dissociation are strongly influenced by the specific hydration sites within the molecular clusters.