Dynamically Hidden Reaction Paths in the Reaction of CF₃ ⁺ + CO

Area of Science:

• Physical Chemistry
• Chemical Dynamics
• Computational Chemistry

Background:

• Potential energy surfaces map chemical reaction pathways.
• Global Reaction Route Mapping (GRRM) automates reaction map construction.
• Understanding reaction dynamics is crucial for interpreting experimental results.

Purpose of the Study:

• Investigate the link between GRRM-predicted reaction paths and actual chemical reaction dynamics.
• Analyze the CF3+ + CO reaction using guided ion beam tandem mass spectrometry (GIBMS).
• Identify discrepancies between theoretical predictions and experimental observations.

Main Methods:

• Guided Ion Beam Tandem Mass Spectrometry (GIBMS) for experimental data.
• Global Reaction Route Mapping (GRRM) for theoretical pathway prediction.
• On-the-fly molecular dynamics simulations to explore reaction mechanisms.

Main Results:

• Observed FCO+, CF2+, and CF+ product ions for CF3+ + CO reaction.
• GRRM predicted CF+ + F2CO channel at 2.5 eV, but experimental threshold was 7.48 eV.
• Molecular dynamics revealed non-statistical energy distribution hides specific reaction paths.

Conclusions:

• Dynamically hidden reaction paths can be inaccessible in experiments at certain energies.
• Reaction dynamics play a critical role in determining chemical reaction outcomes.
• GRRM predictions need to be validated with dynamic simulations and experimental data.