Attosecond Intramolecular Scattering and Vibronic Delays.

We study the temporal and vibrational signature of the universal nuclear recoil associated with the electron emission and intramolecular scattering that accompanies the photoelectric effect. We illustrate these phenomena in the photoionization of the CO molecule from the C-1s orbital using an analytical model that reproduces the entangled character of the nuclear and electronic motion in this process. We show that the photoelectron emission delay can be decomposed into its localization and resonant-confinement components. Photoionization by a broadband x-ray pulse results in a coherent vibrational ionic state delayed compared to the classical sudden-photoemission limit.

Author Correction: Attosecond angular streaking and tunnelling time in atomic hydrogen.

In this Letter, the statement 'I.I. and A.B. performed computations at the NCI Australia' was missing from the Acknowledgements section. This has been corrected online.

Attosecond angular streaking and tunnelling time in atomic hydrogen.

The tunnelling of a particle through a potential barrier is a key feature of quantum mechanics that goes to the core of wave-particle duality. The phenomenon has no counterpart in classical physics, and there are no well constructed dynamical observables that could be used to determine 'tunnelling times'. The resulting debate1-5 about whether a tunnelling quantum particle spends a finite and measurable time under a potential barrier was reignited in recent years by the advent of ultrafast lasers and attosecond metrology6. Particularly important is the attosecond angular streaking ('attoclock') technique7, which can time the release of electrons in strong-field ionization with a precision of a few attoseconds. Initial measurements7-10 confirmed the prevailing view that tunnelling is instantaneous, but later studies11,12 involving multi-electron atoms-which cannot be accurately modelled, complicating interpretation of the ionization dynamics-claimed evidence for finite tunnelling times. By contrast, the simplicity of the hydrogen atom enables precise experimental measurements and calculations13-15 and makes it a convenient benchmark. Here we report attoclock and momentum-space imaging16 experiments on atomic hydrogen and compare these results with accurate simulations based on the three-dimensional time-dependent Schrödinger equation and our experimental laser pulse parameters. We find excellent agreement between measured and simulated data, confirming the conclusions of an earlier theoretical study17 of the attoclock technique in atomic hydrogen that presented a compelling argument for instantaneous tunnelling. In addition, we identify the Coulomb potential as the sole cause of the measured angle between the directions of electron emission and peak electric field: this angle had been attributed11,12 to finite tunnelling times. We put an upper limit of 1.8 attoseconds on any tunnelling delay, in agreement with recent theoretical findings18 and ruling out the interpretation of all commonly used 'tunnelling times'19 as 'time spent by an electron under the potential barrier'20.

Coherent control schemes for the photoionization of neon and helium in the Extreme Ultraviolet spectral region.

The seeded Free-Electron Laser (FEL) FERMI is the first source of short-wavelength light possessing the full coherence of optical lasers, together with the extreme power available from FELs. FERMI provides longitudinally coherent radiation in the Extreme Ultraviolet and soft x-ray spectral regions, and therefore opens up wide new fields of investigation in physics. We first propose experiments exploiting this property to provide coherent control of the photoionization of neon and helium, carry out numerical calculations to find optimum experimental parameters, and then describe how these experiments may be realized. The approach uses bichromatic illumination of a target and measurement of the products of the interaction, analogous to previous Brumer-Shapiro-type experiments in the optical spectral range. We describe operational schemes for the FERMI FEL, and simulate the conditions necessary to produce light at the fundamental and second or third harmonic frequencies, and to control the phase with respect to the fundamental. We conclude that a quantitative description of the phenomena is extremely challenging for present state-of-the-art theoretical and computational methods, and further development is necessary. Furthermore, the intensity available may already be excessive for the experiments proposed on helium. Perspectives for further development are discussed.

Formation of CN

The existence of negative ions in interstellar clouds has been associated for several decades with the process of radiative electron attachment. In this Letter, we report compelling evidence supporting the fact that the radiative attachment of a low-energy electron is inefficient to form the carbon chain anions CN^{-}, C_{3}N^{-}, and C_{5}N^{-} detected in interstellar clouds. The validity of the approach is confirmed by good agreement with experimental data obtained for the inverse photodetachment process, which represents the major cause of anion destruction in interstellar space. As a consequence, we suggest alternative models that could explain the formation of anions.

Theoretical study of radiative electron attachment to CN, C2H, and C4H radicals.

A first-principle theoretical approach to study the process of radiative electron attachment is developed and applied to the negative molecular ions CN(-), C4H(-), and C2H(-). Among these anions, the first two have already been observed in the interstellar space. Cross sections and rate coefficients for formation of these ions by direct radiative electron attachment to the corresponding neutral radicals are calculated. For the CN molecule, we also considered the indirect pathway, in which the electron is initially captured through non-Born-Oppenheimer coupling into a vibrationally resonant excited state of the anion, which then stabilizes by radiative decay. We have shown that the contribution of the indirect pathway to the formation of CN(-) is negligible in comparison to the direct mechanism. The obtained rate coefficients for the direct mechanism at 30 K are 7 × 10(-16) cm(3)/s for CN(-), 7 × 10(-17) cm(3)/s for C2H(-), and 2 × 10(-16) cm(3)/s for C4H(-). These rates weakly depend on temperature between 10 K and 100 K. The validity of our calculations is verified by comparing the present theoretical results with data from recent photodetachment experiments.

Dissociative recombination of highly symmetric polyatomic ions.

A general first-principles theory of dissociative recombination is developed for highly symmetric molecular ions and applied to H(3)O(+) and CH(3)(+), which play an important role in astrophysical, combustion, and laboratory plasma environments. The theoretical cross sections obtained for the dissociative recombination of the two ions are in good agreement with existing experimental data from storage ring experiments.