Disentangling Intracycle Interferences in Photoelectron Momentum Distributions Using Orthogonal Two-Color Laser Fields.

We use orthogonally polarized two-color (OTC) laser pulses to separate quantum paths in the multiphoton ionization of Ar atoms. Our OTC pulses consist of 400 and 800 nm light at a relative intensity ratio of 10∶1. We find a hitherto unobserved interference in the photoelectron momentum distribution, which exhibits a strong dependence on the relative phase of the OTC pulse. Analysis of model calculations reveals that the interference is caused by quantum pathways from nonadjacent quarter cycles.

Duration of an intense laser pulse can determine the breakage of multiple chemical bonds.

Control over the breakage of a certain chemical bond in a molecule by an ultrashort laser pulse has been considered for decades. With the availability of intense non-resonant laser fields it became possible to pre-determine femtosecond to picosecond molecular bond breakage dynamics by controlled distortions of the electronic molecular system on sub-femtosecond time scales using field-sensitive processes such as strong-field ionization or excitation. So far, all successful demonstrations in this area considered only fragmentation reactions, where only one bond is broken and the molecule is split into merely two moieties. Here, using ethylene (C2H4) as an example, we experimentally investigate whether complex fragmentation reactions that involve the breakage of more than one chemical bond can be influenced by parameters of an ultrashort intense laser pulse. We show that the dynamics of removing three electrons by strong-field ionization determines the ratio of fragmentation of the molecular trication into two respectively three moieties. We observe a relative increase of two-body fragmentations with the laser pulse duration by almost an order of magnitude. Supported by quantum chemical simulations we explain our experimental results by the interplay between the dynamics of electron removal and nuclear motion.

Subcycle control of electron-electron correlation in double ionization.

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.

Selective control over fragmentation reactions in polyatomic molecules using impulsive laser alignment.

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.

Attosecond probe of valence-electron wave packets by subcycle sculpted laser fields.

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.

Attosecond-recollision-controlled selective fragmentation of polyatomic molecules.

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.

Effect of laser parameters on ultrafast hydrogen migration in methanol studied by coincidence momentum imaging.

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.

High energy proton ejection from hydrocarbon molecules driven by highly efficient field ionization.

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.

Two-proton migration in 1,3-butadiene in intense laser fields.

Ultrafast proton migration in 1,3-butadiene in an intense laser field (40 fs, 4.5 × 10(14) W cm(-2)) is investigated by using Coulomb explosion coincidence momentum imaging. The spatial distribution maps of a migrating proton reconstructed for the two three-body Coulomb explosion pathways, C(4)H(6)(3+)→ H(+) + CH(3)(+) + C(3)H(2)(+) and C(4)H(6)(3+)→ H(+) + C(2)H(+) + C(2)H(4)(+), reveal that two protons migrate within a 1,3-butadiene molecule, prior to the three body decomposition.