Search Results
Looking inside the tunnelling barrier: II. Co- and counter-rotating electrons at the ‘tunnelling exit’
The initial conditions for electron trajectories at the exit from the tunnelling barrier are often used in strong field models, for example to bridge the first and the second steps of the three-step model celebrated in this issue. Since the analytical R-matrix theory does not rely on the three-step model or the concept of the tunnelling barrier in coordinate space, obtaining the initial conditions for electron trajectories at the barrier exit is, strictly speaking, not necessary to calculate standard observables. Not necessary, but possible—especially when motivated by the occasion of this issue. The opportunity to evaluate such initial conditions emerges as a corollary of analysing sub-barrier kinematics, which includes the interplay of laser and Coulomb fields on the sub-cycle scale (see the companion paper I). We apply our results to discuss the difference in such initial conditions for co- and counter-rotating electrons liberated during strong field ionisation. We derive quantum orbits and classical trajectories describing ionization dynamics of co- and counter-rotating electrons in long-range potentials.
Chiral dichroism in bi-elliptical high-order harmonic generation
The application of strong bi-elliptically polarized laser fields to the generation of high-order harmonics in organic molecules offers exceptional opportunities for chiral recognition and chiral discrimination. These fields are made by combining an elliptically polarized fundamental, typically in the infrared range, with its counter-rotating second harmonic. Here we present a theoretical study of the harmonic emission from the chiral molecule propylene oxide in bi-elliptical fields. Our calculations include, for the first time in such a complex system, accurate photorecomination matrix elements, evaluated using the static-exchange density functional theory method. We show that bi-elliptical light can induce strong chiral dichroism in the harmonic spectra of chiral molecules in a broad range of harmonic numbers and ellipticities.
Recent developments in R-matrix applications to molecular processes
We report on recent developments of the UKRmol suite, an implementation of the molecular R- matrix method and present examples of the calculations (e.g. electron scattering, photoionization, high harmonic generation, etc.) it has enabled.
Coulomb time delays in high harmonic generation
Measuring the time it takes to remove an electron from an atom or molecule during photoionization has been the focus of a number of recent experiments using newly developed attosecond spectroscopies. The interpretation of such measurements, however, depends critically on the measurement protocol and the specific observables available in each experiment. One such protocol relies on high harmonic generation. In this paper, we derive rigorous and general expressions for ionisation and recombination times in high harmonic generation experiments. We show that these times are different from, but related to, ionisation times measured in photoelectron spectroscopy: that is, those obtained using the attosecond streak camera, RABBITT and attoclock methods. We then proceed to use the analytical R-matrix theory to calculate these times and compare them with experimental values.
Roadmap on photonic, electronic and atomic collision physics: I. Light-matter interaction
We publish three Roadmaps on photonic, electronic and atomic collision physics in order to celebrate the 60th anniversary of the ICPEAC conference. In Roadmap I, we focus on the light-matter interaction. In this area, studies of ultrafast electronic and molecular dynamics have been rapidly growing, with the advent of new light sources such as attosecond lasers and x-ray free electron lasers. In parallel, experiments with established synchrotron radiation sources and femtosecond lasers using cutting-edge detection schemes are revealing new scientific insights that have never been exploited. Relevant theories are also being rapidly developed. Target samples for photon-impact experiments are expanding from atoms and small molecules to complex systems such as biomolecules, fullerene, clusters and solids. This Roadmap aims to look back along the road, explaining the development of these fields, and look forward, collecting contributions from twenty leading groups from the field. © 2019 IOP Publishing Ltd.
A molecular clock for autoionization decay
The ultrafast decay of highly excited electronic states is resolved with a molecular clock technique, using the vibrational motion associated to the ionic bound states as a time-reference. We demonstrate the validity of the method in the context of autoionization of the hydrogen molecule, where nearly exact full dimensional ab-initio calculations are available. The vibrationally resolved photoionization spectrum provides a time–energy mapping of the autoionization process into the bound states that is used to fully reconstruct the decay in time. A resolution of a fraction of the vibrational period is achieved. Since no assumptions are made on the underlying coupled electron–nuclear dynamics, the reconstruction procedure can be applied to describe the general problem of the decay of highly excited states in other molecular targets.
Attosecond recorder of the polarization state of light
High harmonic generation in multi-color laser fields opens the opportunity of generating isolated attosecond pulses with high ellipticity. Such pulses hold the potential for time-resolving chiral electronic, magnetization, and spin dynamics at their natural timescale. However, this potential cannot be realized without characterizing the exact polarization state of light on the attosecond timescale. Here we propose and numerically demonstrate a complete solution of this problem. Our solution exploits the extrinsic two-dimensional chirality induced in an atom interacting with the chiral attosecond pulse and a linearly polarized infrared probe. The resulting asymmetry in the photoelectron spectra allows to reconstruct the complete polarization state of the attosecond pulse, including its possible time dependence. The challenging problem of distinguishing circularly polarized, partially polarized, or unpolarized pulses in the extreme ultraviolet range is also resolved. We expect this approach to become the core ingredient for attosecond measurements of chiral-sensitive processes in gas and condensed phase.
Strong-field control and enhancement of chiral response in bi-elliptical high-order harmonic generation: an analytical model
The generation of high-order harmonics in a medium of chiral molecules driven by intense bi-elliptical laser fields can lead to strong chiroptical response in a broad range of harmonic numbers and ellipticities (Ayuso et al 2018 J. Phys. B: At. Mol. Opt. Phys. 51 06LT01). Here we present a comprehensive analytical model that can describe the most relevant features arising in the high-order harmonic spectra of chiral molecules driven by strong bi-elliptical fields. Our model recovers the physical picture underlying chiral high-order harmonic generation (HHG) based on ultrafast chiral hole motion and identifies the rotationally invariant molecular pseudoscalars responsible for chiral dynamics. Using the chiral molecule propylene oxide as an example, we show that one can control and enhance the chiral response in bi-elliptical HHG by tailoring the driving field, in particular by tuning its frequency, intensity and ellipticity, exploiting a suppression mechanism of achiral background based on the linear Stark effect.
NO2molecular frame photoelectron angular distributions for a range of geometries using the R-matrix method
We present R-matrix calculations of photoionization from NO2, resolved in energy, angle, and both neutral and ionic state, for a range of molecular geometries, including in the vicinity of the 2A1/2B2 conical intersection.
Sub-laser-cycle control of coupled electron–nuclear dynamics at a conical intersection
Nonadiabatic processes play a fundamental role in the understanding of photochemical processes in excited polyatomic molecules. A particularly important example is that of radiationless electronic relaxation at conical intersections (CIs). We discuss new opportunities for controlling coupled electron–nuclear dynamics at CIs, offered by the advent of nearly single-cycle, phase-stable, mid-infrared laser pulses. To illustrate the control mechanism, a two-dimensional model of the NO2 molecule is considered. The key idea of the control scheme is to match the time scale of the laser field oscillations to the characteristic time scale of the wave packet transit through the CI. The instantaneous laser field changes the shape and position of the CI as the wave packet passes through. As the CI moves in the laser field, it 'slices' through the wave packet, sculpting it in the coordinate and momentum space in a way that is sensitive to the carrier-envelope phase of the control pulse. We find that the electronic coherence imparted on the sub-laser-cycle time scale manifests during much longer nuclear dynamics that follow on the many tens of femtosecond time scale. Control efficiency as a function of molecular orientation is analyzed, showing that modest alignment is sufficient for showing the described effects.