Factors governing formation from methyl halogens and pseudohalogens.

The formation of following the double ionization of small organic compounds via a roaming mechanism, which involves the generation of H and subsequent proton abstraction, has recently garnered significant attention. Nonetheless, a cohesive model explaining trends in the yield of characterizing these unimolecular reactions is yet to be established. We report yield and femtosecond time-resolved measurements following the strong-field double ionization of CHX molecules, where X = OD, Cl, NCS, CN, SCN, and I.

Femtosecond intramolecular rearrangement of the CHNCS radical cation.

Strong-field ionization, involving tunnel ionization and electron rescattering, enables femtosecond time-resolved dynamics measurements of chemical reactions involving radical cations. Here, we compare the formation of CHS following the strong-field ionization of the isomers CHSCN and CHNCS. The former involves the release of neutral CN, while the latter involves an intramolecular rearrangement.