Felipe Morales

Electron localization following attosecond molecular photoionization

For the past several decades, we have been able to directly probe the motion of atoms that is associated with chemical transformations and which occurs on the femtosecond (10−15-s) timescale. However, studying the inner workings of atoms and molecules on the electronic timescale has become possible only with the recent development of isolated attosecond (10−18-s) laser pulses. Such pulses have been used to investigate atomic photoexcitation and photoionization and electron dynamics in solids, and in molecules could help explore the prompt charge redistribution and localization that accompany photoexcitation processes. In recent work, the dissociative ionization of H2 and D2 was monitored on femtosecond timescales and controlled using few-cycle near-infrared laser pulses. Here we report a molecular attosecond pump–probe experiment based on that work: H2 and D2 are dissociatively ionized by a sequence comprising an isolated attosecond ultraviolet pulse and an intense few-cycle infrared pulse, and a localization of the electronic charge distribution within the molecule is measured that depends—with attosecond time resolution—on the delay between the pump and probe pulses. The localization occurs by means of two mechanisms, where the infrared laser influences the photoionization or the dissociation of the molecular ion. In the first case, charge localization arises from quantum mechanical interference involving autoionizing states and the laser-altered wavefunction of the departing electron. In the second case, charge localization arises owing to laser-driven population transfer between different electronic states of the molecular ion. These results establish attosecond pump–probe strategies as a powerful tool for investigating the complex molecular dynamics that result from the coupling between electronic and nuclear motions beyond the usual Born–Oppenheimer approximation.

The role of the Kramers?Henneberger atom in the higher-order Kerr effect

We present a generalized model for the intensity dependent response of atoms in strong IR laser fields, describing deviations in the nonlinear response at the frequency of the driving field from the standard model (linear Kerr effect + plasma defocusing) based on the formation of the stable KH states. According to our numerical simulations, shaping the driving laser pulse allows one to reveal a prominent resonance structure in the Kerr response of an individual atom, which can only be explained by population transfer into excited KH states.

Imaging the Kramers–Henneberger atom

Today laser pulses with electric fields comparable to or higher than the electrostatic forces binding valence electrons in atoms and molecules have become a routine tool with applications in laser acceleration of electrons and ions, generation of short wavelength emission from plasmas and clusters, laser fusion, etc. Intense fields are also naturally created during laser filamentation in the air or due to local field enhancements in the vicinity of metal nanoparticles. One would expect that very intense fields would always lead to fast ionization of atoms or molecules. However, recently observed acceleration of neutral atoms [Eichmann et al. (2009) Nature 461:1261–1264] at the rate of 1015 m/s2 when exposed to very intense IR laser pulses demonstrated that substantial fraction of atoms remained stable during the pulse. Here we show that the electronic structure of these stable “laser-dressed” atoms can be directly imaged by photoelectron spectroscopy. Our findings open the way to visualizing and controlling bound electron dynamics in strong laser fields and reexamining its role in various strong-field processes, including microscopic description of high order Kerr nonlinearities and their role in laser filamentation [Béjot et al. (2010) Phys Rev Lett 104:103903].

Electron spin polarization in strong-field ionization of xenon atoms

Electron spin polarization is experimentally detected and investigated via strong-field ionization of xenon atoms.

An R-matrix approach to electron–photon–molecule collisions: photoelectron angular distributions from aligned molecules

We present a new extension of the UKRmol electron–molecule scattering code suite, which allows one to compute ab initio photoionization and photorecombination amplitudes for complex molecules, resolved both on the molecular alignment (orientation) and the emission angle and energy of the photoelectron. We illustrate our approach using CO2 as an example, and analyze the importance of multi-channel effects by performing our calculations at different, increasing levels of complexity. We benchmark our method by comparing the results of our calculations with experimental data and with theoretical calculations available in the literature.

Even harmonic generation in isotropic media of dissociating homonuclear molecules.

Isotropic gases irradiated by long pulses of intense IR light can generate very high harmonics of the incident field. It is generally accepted that, due to the symmetry of the generating medium, be it an atomic or an isotropic molecular gas, only odd harmonics of the driving field can be produced. Here we show how the interplay of electronic and nuclear dynamics can lead to a marked breakdown of this standard picture: a substantial part of the harmonic spectrum can consist of even rather than odd harmonics. We demonstrate the effect using ab-initio solutions of the time-dependent Schrödinger equation for and its isotopes in full dimensionality. By means of a simple analytical model, we identify its physical origin, which is the appearance of a permanent dipole moment in dissociating homonuclear molecules, caused by light-induced localization of the electric charge during dissociation. The effect arises for sufficiently long laser pulses and the region of the spectrum where even harmonics are produced is controlled by pulse duration. Our results (i) show how the interplay of femtosecond nuclear and attosecond electronic dynamics, which affects the charge flow inside the dissociating molecule, is reflected in the nonlinear response, and (ii) force one to augment standard selection rules found in nonlinear optics textbooks by considering light-induced modifications of the medium during the generation process.

Attosecond Time-Resolved Electron Dynamics in the Hydrogen Molecule

Recent advances in the generation and characterization of extreme-ultraviolet pulses, generated either by intense femtosecond lasers or by free electron lasers, are pushing the frontier of time-resolved investigations down to the attosecond domain, the relevant timescale for electron motion. The quantum nature of the intertwined electronic and nuclear motion requires theoretical models going beyond the Born-Oppenheimer approximation and taking into account electron correlation, representing a challenge for the computational power available nowadays. Understanding how the electron dynamics inside molecules can influence chemical reactions presents important implications in several fields and allows for the development of new technologies. In this paper, we report on experimental and theoretical results of an investigation in H2/D2, where for the first time control of molecular dynamics with attosecond resolution was achieved. The data represent the first evidence of the control of the electron motion in a molecule undergoing a chemical reaction on the subfemtosecond scale.

Two-photon double ionization of H2 at 30 eV using exterior complex scaling

Calculations of fully differential cross sections for two-photon double ionization of the hydrogen molecule with photons of 30 eV are reported. The results have been obtained by using the method of exterior complex scaling, which allows one to construct essentially exact wavefunctions that describe the double continuum on a large, but finite, volume. The calculated cross sections are compared with those previously obtained by Colgan et al (J. Phys. B: At. Mol. Opt. Phys. 41 121002), and discrepancies are found for specific molecular orientations and electron ejection directions.

Ab initio verification of the analytical R-matrix theory for strong field ionization

We summarize the key aspects of the recently developed analytical R-matrix (ARM) theory for strong field ionization (Torlina and Smirnova 2012 Phys. Rev. A 86 043408; Kaushal and Smirnova 2013 Phys. Rev. A 88 013421), and present tests of this theory using ab initio numerical simulations for hydrogen and helium atoms in long circularly polarized laser pulses. We find excellent agreement between the predictions of ARM and the numerical calculations.

High harmonic spectroscopy of electron localization in the hydrogen molecular ion

Interaction of a laser pulse with a centrally symmetric medium, such as an isotropic gas of atoms, leads to the generation of harmonic emission which contains exclusively odd harmonics of the incident field. This result is the consequence of both the central symmetry of the medium and the temporal symmetry of the oscillating electric field, , where ωl is the laser frequency. In the case of oriented heteronuclear molecules, the spatial symmetry no longer holds and both odd and even harmonics become allowed. Here we show, by solving the time-dependent Schrodinger equation for H, D, and T, that even-order harmonic generation is also possible for sufficiently long infrared (IR) laser pulses in homonuclear molecules. The appearance of even harmonics is a signature of the coupled electron-nuclear dynamics and reflects field-induced electron localization initiated by the strong laser field, which breaks the spatial symmetry in the system. The analysis of even harmonics generated by pulses of different durations might therefore provide information on correlated electron-nuclear dynamics and charge migration in more complex un-oriented molecular ensembles.