Ali Sami Alnaser

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-tagged imaging of the controlled electron acceleration from SiO2 nanospheres in intense few-cycle laser fields

Waveform-controlled light fields offer the possibility of manipu- lating ultrafast electronic processes on sub-cycle timescales. The optical light- wave control of the collective electron motion in nanostructured materials is key to the design of electronic devices operating at up to petahertz frequencies. We have studied the directional control of the electron emission from 95nm 10 Authors to whom any correspondence should be addressed.

Strong-field control of the dissociative ionization of N2O with near-single-cycle pulses

The dissociative ionization of N2O by near-single-cycle laser pulses is studied using phase-tagged ion–ion coincidence momentum imaging. Carrier–envelope phase (CEP) dependences are observed in the absolute ion yields and the emission direction of nearly all ionization and dissociation pathways of the triatomic molecule. We find that laser-field-driven electron recollision has a significant impact on the dissociative ionization dynamics and results in pronounced CEP modulations in the dication yields, which are observed in the product ion yields after dissociation. The results indicate that the directional emission of coincident + N and + NO ions in the denitrogenation of the dication can be explained by selective ionization of oriented molecules. The deoxygenation of the dication with the formation of coincident + N 2 + + O ions exhibits an additional shift in its CEP dependence, suggesting that this channel is further influenced by laser interaction with the dissociating dication. The experimental

Steering Proton Migration in Hydrocarbons Using Intense Few-Cycle Laser Fields

Proton migration is a ubiquitous process in chemical reactions related to biology, combustion, and catalysis. Thus, the ability to manipulate the movement of nuclei with tailored light within a hydrocarbon molecule holds promise for far-reaching applications. Here, we demonstrate the steering of hydrogen migration in simple hydrocarbons, namely, acetylene and allene, using waveform-controlled, few-cycle laser pulses. The rearrangement dynamics is monitored using coincident 3D momentum imaging spectroscopy and described with a widely applicable quantum-dynamical model. Our observations reveal that the underlying control mechanism is due to the manipulation of the phases in a vibrational wave packet by the intense off-resonant laser field.

Intensity dependence of the attosecond control of the dissociative ionization of D2

Light-field driven electron localization in deuterium molecules in intense near single-cycle laser fields is studied as a function of the laser intensity. The emission of D+ ions from the dissociative ionization of D2 is interrogated with single-shot carrier–envelope phase (CEP)-tagged velocity map imaging. We explore the reaction for an intensity range of (1.0–2.8) × 1014 W cm−2, where laser-driven electron recollision leads to the population of excited states of D2+. Within this range we find the onset of dissociation from 3σ states of D2+ by comparing the experimental data to quantum dynamical simulations including the first eight states of D2+. We find that dissociation from the 3σ states yields D+ ions with kinetic energies above 8 eV. Electron localization in the dissociating molecule is identified through an asymmetry in the emission of D+ ions with respect to the laser polarization axis. The observed CEP-dependent asymmetry indicates two mechanisms for the population of 3σ states: (1) excitation by electron recollision to the lower excited states, followed by laser-field excitation to the 3σ states, dominating at low intensities, and (2) direct excitation to the 3σ states by electron recollision, playing a role at higher intensities.

Strong-field non-sequential double ionization: wavelength dependence of ion momentum distributions for neon and argon

Strong-field double ionization of atoms in a non-sequential regime produces longitudinal ion momentum distributions with a characteristic double-peak structure. At 800 nm laser wavelength in Ne2+ the structure is very pronounced with a well-resolved dip at zero momentum, while for Ar2+ the dip is very shallow, possibly indicating different mechanisms in the two atoms. We investigated the source of this difference by measuring longitudinal momentum distributions of Ne2+ and Ar2+ ions at different laser wavelengths (485, 800, 1313 and 2000 nm) and intensities. The shapes of the experimental momentum distributions for the two atoms exhibit strong dependence on laser wavelength: for both the dip becomes more pronounced at longer wavelengths. At 1300 nm the longitudinal momentum spectrum for Ar2+ is similar to that of Ne2+ at 800 nm. On the other hand, the Ne2+ spectrum measured at 485 nm has the same shape as that of Ar2+ at 800 nm. This observation indicates that the difference between Ne and Ar observed at 800 nm should not be attributed solely to differences in relative electron impact ionization and excitation cross-sections of the two atoms. It is, to a larger extent, due to the interplay between the ponderomotive energy of electron and the ionization potentials of the target atom.

Coherent control of D2/H2 dissociative ionization by a mid-infrared two-color laser field

Steering the electrons during an ultrafast photo-induced process in a molecule influences the chemical behavior of the system, opening the door to the control of photochemical reactions and photobiological processes. Electrons can be efficiently localized using a strong laser field with a well-designed temporal shape of the electric component. Consequently, many experiments have been performed with laser sources in the near-infrared region (800 nm) in the interest of studying and enhancing the electron localization. However, due to its limited accessibility, the mid-infrared (MIR) range has barely been investigated, although it allows to efficiently control small molecules and even more complex systems. To push further the manipulation of basic chemical mechanisms, we used a MIR two-color (1800 and 900 nm) laser field to ionize H2 and D2 molecules and to steer the remaining electron during the photo-induced dissociation. The study of this prototype reaction led to the simultaneous control of four fragmentation channels. The results are well reproduced by a theoretical model solving the time-dependent Schrodinger equation for the molecular ion, identifying the involved dissociation mechanisms. By varying the relative phase between the two colors, asymmetries (i.e., electron localization selectivity) of up to 65% were obtained, corresponding to enhanced or equivalent levels of control compared to previous experiments. Experimentally easier to implement, the use of a two-color laser field leads to a better electron localization than carrier-envelope phase stabilized pulses and applying the technique in the MIR range reveals more dissociation channels than at 800 nm.

Wavelength-dependent study of strong-field Coulomb explosion of hydrogen

We present the first systematic wavelength-dependent study of laser Coulomb explosion of deuterium molecules at various peak intensities and polarizations. We measured the kinetic energy spectra of D+ for laser wavelengths in the range 480–2000 nm. In addition to the well-known enhanced ionization channel present for all wavelengths, we observe a new high-energy band at short wavelengths. This new band exhibits wavelength dependence, with fragment energy decreasing with increasing wavelengths until it merges with the enhanced ionization band for 800 nm and longer. We attribute the emergence of this band to a new pathway that involves resonant three-photon coupling to the first excited electronic state of the molecular ion during the Coulomb explosion process. This pathway should be accounted for in controlling molecular dynamics of hydrogen by intense laser pulses.

Visualization of bond rearrangements in acetylene using near single-cycle laser pulses

The migration of hydrogen atoms resulting in the isomerization of hydrocarbons is an important process which can occur on ultrafast timescales. Here, we visualize the light-induced hydrogen migration of acetylene to vinylidene in an ionic state using two synchronized 4 fs intense laser pulses. The first pulse induces hydrogen migration, and the second is used for monitoring transient structural changes via Coulomb explosion imaging. Varying the time delay between the pulses reveals the migration dynamics with a time constant of 54 ± 4 fs as observed in the H+ + H+ + CC+ channel. Due to the high temporal resolution, vibrational wave-packet motions along the CC- and CH-bonds are observed. Even though a maximum in isomerization yield for kinetic energy releases above 16 eV is measured, we find no indication for a backwards isomerization - in contrast to previous measurements. Here, we propose an alternative explanation for the maximum in isomerization yield, namely the surpassing of the transition state to the vinylidene configuration within the excited dication state.

Time-resolved nuclear dynamics in bound and dissociating acetylene

We have investigated nuclear dynamics in bound and dissociating acetylene molecular ions in a time-resolved reaction microscopy experiment with a pair of few-cycle pulses. Vibrating bound acetylene cations or dissociating dications are produced by the first pulse. The second pulse probes the nuclear dynamics by ionization to higher charge states and Coulomb explosion of the molecule. For the bound cations, we observed vibrations in acetylene (HCCH) and its isomer vinylidene (CCHH) along the CC-bond with a periodicity of around 26 fs. For dissociating dication molecules, a clear indication of enhanced ionization is found to occur along the CH- and CC-bonds after 10 fs to 40 fs. The time-dependent ionization processes are simulated using semi-classical on-the-fly dynamics revealing the underling mechanisms.