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Abstract Roaming is an unconventional type of molecular reaction where fragments, instead of immediately dissociating, remain weakly bound due to long-range Coulombic interactions. Due to its prevalence and ability to form new molecular compounds, roaming is fundamental to photochemical reactions in small molecules. However, the neutral character of the roaming fragment and its indeterminate trajectory make it difficult to identify experimentally. Here, we introduce an approach to image roaming, utilizing intense, femtosecond IR radiation combined with Coulomb explosion imaging to directly reconstruct the momentum vector of the neutral roaming H₂, a precursor to$${{{{{{{{\rm{H}}}}}}}}_{3}}^{+}$$ ${H_3}^{+}$formation, in acetonitrile, CH₃CN. This technique provides a kinematically complete picture of the underlying molecular dynamics and yields an unambiguous experimental signature of roaming. We corroborate these findings with quantum chemistry calculations, resolving this unique dissociative process. 

Upon photoexcitation, molecules can undergo numerous complex processes, such as isomerization and roaming, leading to changes in the molecular and electronic structure. Here, we report on the time-resolved ultrafast nuclear dynamics, initiated by laser ionization, in the two structural isomers, 1- and 2-propanol, using a combination of pump–probe spectroscopy and coincident Coulomb explosion imaging. Our measurements, paired with quantum chemistry calculations, identify the mechanisms for the observed two- and three-body dissociation channels for both isomers. In particular, the fragmentation channel of 2-propanol associated with the loss of CH 3 shows possible evidence of methyl roaming. Moreover, the electronic structure of this roaming methyl fragment could be responsible for the enhanced ionization also observed for this channel. Finally, comparison with similar studies done on ethanol and acetonitrile helps establish a correlation between the length of the alkyl chain and the likelihood of hydrogen migration.