Photodissociation Pathways of Methanol: Dissociation, Roaming, and Migration
Year: 2025
Type: article
Abstract: In this joint experimental and theoretical study, we examine the two-body photodissociation pathways induced in deuterated methanol by both single and double laser pulses. The measurements were conducted using IR pump–IR probe spectroscopy paired with the coincident momentum imaging technique. Our work unambiguously shows the roaming behavior of a D 2 neutral resulting in D 2 +, which is a strong pathway after direct excitation to a dication. Two pulse measurements reveal that despite the low formation probability, the migration pathways occur fastest of any photodissociation relaxation route. To elucidate the mechanistic origin of the observed fragmentation channels, we performed ab initio molecular dynamics simulations based on DFT for ground-state reactivity and state-averaged CASSCF for excited-state dynamics, enabling direct comparison with experimental yields.
Authors: Noah Frese, Debadarshini Mishra, Clark Bray, Cameron Brady, Aaron C. LaForge, Angelo R. Rossi, José A. Gascón, Nora Berrah
Institution: University of Connecticut
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funder: Division of Physics
Award: G4975400392
OpenAlex ID: W4415473661