The importance of Rydberg orbitals in dissociative ionization of small hydrocarbon molecules in intense laser fields.

Much of our intuition about strong-field processes is built upon studies of diatomic molecules, which typically have electronic states that are relatively well separated in energy. In polyatomic molecules, however, the electronic states are closer together, leading to more complex interactions. A combined experimental and theoretical investigation of strong-field ionization followed by hydrogen elimination in the hydrocarbon series C2D2, C2D4 and C2D6 reveals that the photofragment angular distributions can only be understood when the field-dressed orbitals rather than the field-free orbitals are considered. Our measured angular distributions and intensity dependence show that these field-dressed orbitals can have strong Rydberg character for certain orientations of the molecule relative to the laser polarization and that they may contribute significantly to the hydrogen elimination dissociative ionization yield. These findings suggest that Rydberg contributions to field-dressed orbitals should be routinely considered when studying polyatomic molecules in intense laser fields.

Transition from SAMO to Rydberg State Ionization in C60 in Femtosecond Laser Fields.

The transition between two distinct ionization mechanisms in femtosecond laser fields at 785 nm is observed for C60 molecules. The transition occurs in the investigated intensity range from 3 to 20 TW/cm2 and is visualized in electron kinetic energy spectra below the one-photon energy (1.5 eV) obtained via velocity map imaging. Assignment of several observed broad spectral peaks to ionization from superatom molecular orbitals (SAMOs) and Rydberg states is based on time-dependent density functional theory simulations. We find that ionization from SAMOs dominates the spectra for intensities below 5 TW/cm2. As the intensity increases, Rydberg state ionization exceeds the prominence of SAMOs. Using short laser pulses (20 fs) allowed uncovering of distinct six-lobe photoelectron angular distributions with kinetic energies just above the threshold (below 0.2 eV), which we interpret as over-the-barrier ionization of shallow f-Rydberg states in C60.

Subfemtosecond steering of hydrocarbon deprotonation through superposition of vibrational modes.

Subfemtosecond control of the breaking and making of chemical bonds in polyatomic molecules is poised to open new pathways for the laser-driven synthesis of chemical products. The break-up of the C-H bond in hydrocarbons is an ubiquitous process during laser-induced dissociation. While the yield of the deprotonation of hydrocarbons has been successfully manipulated in recent studies, full control of the reaction would also require a directional control (that is, which C-H bond is broken). Here, we demonstrate steering of deprotonation from symmetric acetylene molecules on subfemtosecond timescales before the break-up of the molecular dication. On the basis of quantum mechanical calculations, the experimental results are interpreted in terms of a novel subfemtosecond control mechanism involving non-resonant excitation and superposition of vibrational degrees of freedom. This mechanism permits control over the directionality of chemical reactions via vibrational excitation on timescales defined by the subcycle evolution of the laser waveform.

Carrier-envelope phase control over pathway interference in strong-field dissociation of H2+.

The dissociation of an H2+ molecular-ion beam by linearly polarized, carrier-envelope-phase-tagged 5 fs pulses at 4×10(14) W/cm2 with a central wavelength of 730 nm was studied using a coincidence 3D momentum imaging technique. Carrier-envelope-phase-dependent asymmetries in the emission direction of H+ fragments relative to the laser polarization were observed. These asymmetries are caused by interference of odd and even photon number pathways, where net zero-photon and one-photon interference predominantly contributes at H+ + H kinetic energy releases of 0.2-0.45 eV, and net two-photon and one-photon interference contributes at 1.65-1.9 eV. These measurements of the benchmark H2+ molecule offer the distinct advantage that they can be quantitatively compared with ab initio theory to confirm our understanding of strong-field coherent control via the carrier-envelope phase.

Directional emission of multiply charged ions during dissociative ionization in asymmetric two-color laser fields.

Intense, asymmetric 1ω+2ω laser fields are used to affect the directional ejection of multiply charged ion fragments from a variety of molecules, including N2, O2, CO, HBr, and CO2. By tuning the relative phase, ϕ, between the two fields, we observe large forward-backward dissociation asymmetries. The largest asymmetries are obtained at the same values of ϕ for all species, suggesting a common dynamical mechanism. Following an independent phase calibration, the sign of the asymmetry appears to be opposite that expected from the standard enhanced ionization model.