Control over various fragmentation reactions of a series of polyatomic molecules (acetylene, ethylene, 1,3-butadiene) by the optical waveform of intense few-cycle laser pulses is demonstrated experimentally. We show both experimentally and theoretically that the responsible mechanism is inelastic ionization from inner-valence molecular orbitals by recolliding electron wave packets, whose recollision energy in few-cycle ionizing laser pulses strongly depends on the optical waveform. Our work demonstrates an efficient and selective way of predetermining fragmentation and isomerization reactions in polyatomic molecules on subfemtosecond time scales.

We experimentally and theoretically demonstrate a self-referenced wave-function retrieval of a valence-electron wave packet during its creation by strong-field ionization with a sculpted laser field. Key is the control over interferences arising at different time scales. Our work shows that the measurement of subcycle electron wave-packet interference patterns can serve as a tool to retrieve the structure and dynamics of the valence-electron cloud in atoms on a sub-10-as time scale.

We investigated the ejection of energetic protons from a series of polyatomic hydrocarbon molecules exposed to 790 nm 27 fs laser pulses. Using multiparticle coincidence imaging we were able to decompose the observed proton energy spectra into the contributions of individual fragmentation channels. It is shown that the molecules can completely fragment already at relatively low peak intensities of a few 10(14)  W/cm(2), and that the protons are ejected in a concerted Coulomb explosion from unexpectedly high charge states. The observations are in agreement with enhanced ionization taking place at many C-H bonds in parallel.

Double ionization of neon with orthogonally polarized two-color (OTC) laser fields is investigated using coincidence momentum imaging. We show that the two-electron emission dynamics in nonsequential double ionization can be controlled by tuning the subcycle shape of the electric field of the OTC pulses. We demonstrate experimentally switching from correlated to anticorrelated two-electron emission, and control over the directionality of the two-electron emission. Simulations based on a semiclassical trajectory model qualitatively explain the experimental results by a subcycle dependence of the electron recollision time on the OTC field shape.

We investigate the possibility of using molecular alignment for controlling the relative probability of individual reaction pathways in polyatomic molecules initiated by electronic processes on the few-femtosecond time scale. Using acetylene as an example, it is shown that aligning the molecular axis with respect to the polarization direction of the ionizing laser pulse does not only allow us to enhance or suppress the overall fragmentation yield of a certain fragmentation channel but, more importantly, to determine the relative probability of individual reaction pathways starting from the same parent molecular ion. We show that the achieved control over dissociation or isomerization pathways along specific nuclear degrees of freedom is based on a controlled population of associated excited dissociative electronic states in the molecular ion due to relatively enhanced ionization contributions from inner valence orbitals.

We experimentally investigate the dependence of the fragmentation behavior of the ethylene dication on the intensity and duration of the laser pulses that initiate the fragmentation dynamics by strong-field double ionization. Using coincidence momentum imaging for the detection of ionic fragments, we disentangle the different contributions of ionization from lower-valence orbitals and field-driven excitation dynamics to the population of certain dissociative excited ionic states that are connected to one of several possible fragmentation pathways towards a given set of fragment ions. We find that the excitation probability to a particular excited state and therewith the outcome of the fragmentation reaction strongly depend on the parameters of the laser pulse. This, in turn, opens up new possibilities for controlling the outcome of fragmentation reactions of polyatomic molecules in that it may allow one to selectively enhance or suppress individual fragmentation channels, which was not possible in previous attempts of controlling fragmentation processes of polyatomic molecules with strong laser fields.

The effect of intensity, duration, and polarization of ultrashort laser pulses (795 nm, 40-100 fs, and 0.15-1.5 × 10(15) W/cm(2)) on the hydrogen migration in methanol is systematically investigated using Coulomb explosion coincidence momentum imaging. The ratio of the ion yield obtained for the migration pathway CH(3)OH(2+) → CH(2)(+) + OH(2)(+) with respect to the sum of the yields obtained for the migration pathway and for the nonmigration pathway CH(3)OH(2+) → CH(3)(+) + OH(+) exhibits a small (10-20%) but clear dependence on laser pulse properties, that is, the ratio decreases as the laser peak intensity increases but increases when the pulse duration increases as well as when the laser polarization is changed from linear to circular.

Interpretation of electron or photon spectra obtained with strong laser pulses that may carry attosecond dynamical and Ångström structural information about atoms or molecules usually relies on variants of the strongfield approximation (SFA) within which the influence of the Coulomb potential on the electron trajectory is neglected. We employ two-color sculpted laser fields to experimentally tune and probe the influence of the Coulomb field on the strong-field-driven wavepacket as observed by two-dimensional electron and ion momentum spectra. By comparison of measured spectra with predictions of the three-dimensional time-dependent Schrödinger equation as well as the quasiclassical limit of the SFA, the strong-field classical trajectory model, we are able to trace back the influence of the Coulomb field to the timing of the wavepacket release with sub-cycle precision.