Theoretical and experimental studies on hydrogen migration in dissociative ionization of the methanol monocation to molecular ions H3 + and H2O.

The dissociative ionization processes of the methanol monocation CH3OH+ to H3 + + CHO and H2O+ + CH2 are studied by ab initio method, and hydrogen migration processes are confirmed in these two dissociation processes. Due to the positive charge assignment in dissociation processes, the fragmentation pathways of CH3OH+ to H3 + CHO+ and CH3OH+ to H2O + CH2 + are also calculated. The calculation results show that a neutral H2 moiety in the methanol monocation CH3OH+ is the origin of the formation of H3 +, and the ejection of fragment ions H3 + and H2O+ is more difficult than CHO+ and CH2 + respectively. Experimentally, by using a dc-slice imaging technique under an 800 nm femtosecond laser field, the velocity distributions of fragment ions H3 +, CHO+, CH2 +, and H2O+ are calculated from their corresponding sliced images. The presence of low-velocity components of these four fragment ions confirms that the formation of these ions is not from the Coulomb explosion of the methanol dication. Hence, the four hydrogen migration pathways from the methanol monocation CH3OH+ to H3 + + CHO, CHO+ + H3, H2O+ + CH2, and CH2 + + H2O are securely confirmed. It can be observed in the time-of-flight mass spectrum of ionization and dissociation of methanol that the ion yields of fragment ions H3 + and H2O+ are lower than CHO+ and CH2 + respectively, which is consistent with the theoretical results according to which dissociation from the methanol monocation to H3 + and H2O+ is more difficult than CHO+ and CH2 + respectively.