Chirality causes symmetry breaks in a large variety of natural phenomena ranging from particle physics to biochemistry. We investigate one of the simplest conceivable chiral systems, a laser-excited, oriented, effective one-electron Li target. Prepared in a polarized p state with |m|=1 in an optical trap, the atoms are exposed to co- and counterrotating circularly polarized femtosecond laser pulses. For a field frequency near the excitation energy of the oriented initial state, a strong circular dichroism is observed and the photoelectron energies are significantly affected by the helicity-dependent Autler-Townes splitting. Besides its fundamental relevance, this system is suited to create spin-polarized electron pulses with a reversible switch on a femtosecond timescale at an energy resolution of a few meV.
We propose an attosecond extreme ultraviolet pump IR-probe photoionization protocol that employs pairs of counterrotating consecutive harmonics and angularly resolved photoelectron detection, thereby providing a direct measurement of ionization phases. The present method, which we call circular holographic ionization-phase meter, gives also access to the phase of photoemission amplitudes of even-parity continuum states from a single time-delay measurement since the relative phase of one- and two-photon ionization pathways is imprinted in the photoemission anisotropy. The method is illustrated with ab initio simulations of photoionization via autoionizing resonances in helium. The rapid phase excursion in the transition amplitude to both the dipole-allowed (2s2p)^{1}P^{o} and the dipole-forbidden (2p^{2})^{1}D^{e} states are faithfully reproduced.
The complex Kohn variational method is extended to compute light-driven electronic transitions between continuum wave functions in atomic and molecular systems. This development enables the study of multiphoton processes in the perturbative regime for arbitrary light polarization. As a proof of principle, we apply the method to compute the photoelectron spectrum arising from the pump-probe two-photon ionization of helium induced by a sequence of extreme ultraviolet and infrared light pulses. We compare several two-photon ionization pump-probe spectra, resonant with the (2s2p) 1 P 1 o Feshbach resonance, with independent simulations based on the atomic B-spline close-coupling STOCK code, and find good agreement between the two approaches. This finite-pulse perturbative approach is a step towards the ab initio study of weak-field attosecond processes in polyelectronic molecules.
Intense, circularly polarized extreme-ultraviolet and near-infrared (NIR) laser pulses are combined to double ionize atomic helium via the oriented intermediate He^{+}(3p) resonance state. Applying angle-resolved electron spectroscopy, we find a large photon helicity dependence of the spectrum and the angular distribution of the electrons ejected from the resonance by NIR multiphoton absorption. The measured circular dichroism is unexpectedly found to vary strongly as a function of the NIR intensity. The experimental data are well described by theoretical modeling and possible mechanisms are discussed.
We present a combined experimental and theoretical investigation of the dynamics and angular dependence of dissociative electron attachment to methane. We show that a triply degenerate (T2) Feshbach resonance is responsible for the broad 10 eV dissociation peak in methane. This resonance alone is shown to correlate asymptotically to the various dissociation channels observed experimentally. The molecular-frame entrance amplitude for electron attachment is calculated for each component of the threefold degenerate resonance. By investigating the topology of the anion potential energy surfaces, we deduce the main pathways to two- and three-body breakup channels involving both bond scission and bond formation. The computed fragment angular distributions reproduce the main trends of the experimental measurements.
Methane/chemistry , Anions/chemistry , Electrons , Models, Chemical
We present a theoretical study of the indirect dissociative recombination of linear polyatomic ions at low collisional energies. The approach is based on the computation of the scattering matrix just above the ionization threshold and enables the explicit determination of all diabatic electronic couplings responsible for dissociative recombination. In addition, we use the multi-channel quantum-defect theory to demonstrate the precision of the scattering matrix by reproducing accurately ab initio Rydberg state energies of the neutral molecule. We consider the molecular ions N2H(+) and HCO(+) as benchmark systems of astrophysical interest and improve former theoretical studies, which had repeatedly produced smaller cross sections than experimentally measured. Specifically, we demonstrate the crucial role of the previously overlooked stretching modes for linear polyatomic ions with large permanent dipole moment. The theoretical cross sections for both ions agree well with experimental data over a wide energy range. Finally, we consider the potential role of the HOC(+) isomer in the experimental cross sections of HCO(+) at energies below 10 meV.
