Hydrogen migration in inner-shell ionized halogenated cyclic hydrocarbons.

We have studied the fragmentation of the brominated cyclic hydrocarbons bromocyclo-propane, bromocyclo-butane, and bromocyclo-pentane upon Br(3d) and C(1s) inner-shell ionization using coincidence ion momentum imaging. We observe a substantial yield of CH3+ fragments, whose formation requires intramolecular hydrogen (or proton) migration, that increases with molecular size, which contrasts with prior observations of hydrogen migration in linear hydrocarbon molecules. Furthermore, by inspecting the fragment ion momentum correlations of three-body fragmentation channels, we conclude that CHx+ fragments (with x = 0, …, 3) with an increasing number of hydrogens are more likely to be produced via sequential fragmentation pathways. Overall trends in the molecular-size-dependence of the experimentally observed kinetic energy releases and fragment kinetic energies are explained with the help of classical Coulomb explosion simulations.

Ultrafast molecular dynamics in ionized 1- and 2-propanol: from simple fragmentation to complex isomerization and roaming mechanisms.

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 CH3 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.

Resonance-Enhanced Multiphoton Ionization in the X-Ray Regime.

Here, we report on the nonlinear ionization of argon atoms in the short wavelength regime using ultraintense x rays from the European XFEL. After sequential multiphoton ionization, high charge states are obtained. For photon energies that are insufficient to directly ionize a 1s electron, a different mechanism is required to obtain ionization to Ar^{17+}. We propose this occurs through a two-color process where the second harmonic of the FEL pulse resonantly excites the system via a 1s→2p transition followed by ionization by the fundamental FEL pulse, which is a type of x-ray resonance-enhanced multiphoton ionization (REMPI). This resonant phenomenon occurs not only for Ar^{16+}, but also through lower charge states, where multiple ionization competes with decay lifetimes, making x-ray REMPI distinctive from conventional REMPI. With the aid of state-of-the-art theoretical calculations, we explain the effects of x-ray REMPI on the relevant ion yields and spectral profile.

Ultrafast Laser-Induced Isomerization Dynamics in Acetonitrile.

Isomerization induced by laser ionization in acetonitrile (CH3CN) was investigated using pump-probe spectroscopy in combination with ion-ion coincident Coulomb explosion imaging. We deduced five primary channels indicating direct C-C breakup, single and double hydrogen migration, and H and H2 dissociation in the acetonitrile cation. Surprisingly, the hydrogen-migration channels dominate over direct fragmentation. This observation is supported by quantum chemistry calculations showing that isomerization through single and double hydrogen migration leads to very stable linear and ring isomers, with most of them more stable than the original linear structure following ionization of the parent molecule. This is unlike most molecules investigated previously using similar schemes. By varying the delay between the pump and probe pulses, we have also determined the time scales of the corresponding dynamical processes. Isomerization typically occurs in a few hundred femtoseconds, a time scale that is comparable to that found for H and H2 dissociation and direct molecular fragmentation.