Using isotopologues to probe the potential energy surface of reactions of C2H2++C3H4

Investigations into bimolecular reaction kinetics probe the details of the underlying potential energy surface (PES), which can help to validate high-level quantum chemical calculations. We utilize a combined linear Paul ion trap with a time-of-flight mass spectrometer to study isotopologue reaction...

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Bibliographic Details
Published in:The Journal of chemical physics 2021-03, Vol.154 (12), p.124310-124310
Main Authors: Greenberg, James, Schmid, Philipp C., Thorpe, James H., Nguyen, Thanh L., Catani, Katherine J., Krohn, Olivia A., Miller, Mikhail I., Stanton, John F., Lewandowski, H. J.
Format: Article
Language:English
Subjects:
Acetylene
Allene
Charge exchange
Isomers
Laser cooling
Mathematical analysis
Potential energy
Quantum chemistry
Reaction kinetics
Reaction mechanisms
Substitution reactions
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Summary:Investigations into bimolecular reaction kinetics probe the details of the underlying potential energy surface (PES), which can help to validate high-level quantum chemical calculations. We utilize a combined linear Paul ion trap with a time-of-flight mass spectrometer to study isotopologue reactions between acetylene cations (C2H2+) and two isomers of C3H4: propyne (HC3H3) and allene (H2C3H2). In a previous study [Schmid et al., Phys. Chem. Chem. Phys. 22, 20303 (2020)],1 we showed that the two isomers of C3H4 have fundamentally different reaction mechanisms. Here, we further explore the calculated PES by isotope substitution. While isotopic substitution of reactants is a standard experimental tool in the investigation of molecular reaction kinetics, the controlled environment of co-trapped, laser-cooled Ca+ ions allows the different isotopic reaction pathways to be followed in greater detail. We report branching ratios for all of the primary products of the different isotopic species. The results validate the previously proposed mechanism: propyne forms a bound reaction complex with C2H2+, while allene and C2H2+ perform long-range charge exchange only.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0046438