Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here, the mechanistic details and femtosecond time-resolved dynamics of H3+ formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H2 roaming prior to H3+ formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H3+ formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H3+, the most important ion in interstellar chemistry, through H2 roaming occurring in ionic species.

Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. We present evidence for the existence of two different reaction pathways for H3 + formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followed by the abstraction of a proton from the remaining CHOH2+ fragment by the roaming H2 molecule. This reaction has similarities to the H2 + H2 + mechanism leading to formation of H3 + in the universe. These exotic chemical reaction mechanisms, involving roaming H2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.

Laser-induced dissociation and ionization of H(+)(2) were simultaneously measured using coincidence 3D momentum imaging, allowing direct separation of the two processes, even where the fragment kinetic energy is the same for both processes. The results for 45 and 135 fs 790 nm pulses with an intensity of approximately 2.5 x 10(14) W/cm(2) differ from each other much more than one would expect from previous measurements with longer pulses. Ionization was negligible for the longer pulse and was strongly aligned along the laser polarization for the shorter pulse, but showed no structure in its kinetic energy distribution. In addition, the ionization to dissociation ratio was found to be much smaller than theoretically predicted for H(+)(2).

The H(3)(+) ion is the simplest polyatomic molecule and is destined to play a central role in understanding such molecules in intense ultrashort laser pulses. We present the first measurements of the intense field dissociation and ionization of D(3)(+) using coincidence three-dimensional momentum imaging. Our results show features that are a consequence of this molecule's unique equilateral triangular geometry, providing a fundamentally new system for theoretical development.

The dissociation of H 2 + in an intense laser field has been experimentally studied using femtosecond laser pulses at 790 nm in the intensity range of 10 13 -10 15 W/cm 2 . Kinematically complete measurements of both the ionic H + and neutral H fragments dissociated from a vibrationally excited H 2 + beam have been achieved by a coincidence three-dimensional momentum imaging system. Angular-resolved kinetic energy release spectra for a series of different intensity ranges have been obtained using the intensity-difference spectrum method, thus disentangling the problem caused by the intensity volume effect. Our results indicate that the dissociation dynamics are drastically different for "long" ͑135 fs͒ and "short" ͑45 fs͒ laser pulses at similar high laser intensities. Specifically, bond softening is found to be the main feature in long pulses, while above threshold dissociation is dominant in short pulses whose durations are comparable with the vibrational period of the molecule. Bond softening in short pulses appears at low kinetic energy release with a narrow angular distribution. The experimental results are well interpreted by solving the time-dependent Schrödinger equation in the Born-Oppenheimer representation without nuclear rotation.