Electronic movement flashing into view: Numerous chemical processes begin with ionization: the ejection of an electron from a molecule. What happens in the immediate aftermath of that event? Kraus et al. explored this question in iodoacetylene by detecting and analyzing the spectrum of emitted high harmonics (see the Perspective by Ueda). They traced the migration of the residual positively charged hole along the molecular axis on a time scale faster than a quadrillionth of a second. They thereby characterized the capacity of a laser field to steer the hole's motion in appropriately oriented molecules. Science , this issue p. 790 ; see also p. 740

We study the emission of even and odd high-harmonic orders from oriented OCS molecules. We use an intense, nonresonant femtosecond laser pulse superimposed with its phase-controlled second harmonic field to impulsively align and orient a dense sample of molecules from which we subsequently generate high-order harmonics. The even harmonics appear around the full revivals of the rotational dynamics. We demonstrate perfect coherent control over their intensity through the subcycle delay of the two-color fields. The odd harmonics are insensitive to the degree of orientation, but modulate with the degree of axis alignment, in agreement with calculated photorecombination dipole moments. We further compare the shape of the even and odd harmonic spectra with our calculations and determine the degree of orientation.

All attosecond time-resolved measurements have so far relied on the use of intense near-infrared laser pulses. In particular, attosecond streaking, laser-induced electron diffraction and high-harmonic generation all make use of non-perturbative light–matter interactions. Remarkably, the effect of the strong laser field on the studied sample has often been neglected in previous studies. Here we use high-harmonic spectroscopy to measure laser-induced modifications of the electronic structure of molecules. We study high-harmonic spectra of spatially oriented CH₃F and CH₃Br as generic examples of polar polyatomic molecules. We accurately measure intensity ratios of even and odd-harmonic orders, and of the emission from aligned and unaligned molecules. We show that these robust observables reveal a substantial modification of the molecular electronic structure by the external laser field. Our insights offer new challenges and opportunities for a range of emerging strong-field attosecond spectroscopies.

Protonated dialanine cations have been isolated in a Fourier transform ion cyclotron resonance mass-spectrometer (FT-ICR-MS) and subjected to infrared multiphoton dissociation (IRMPD) at the free electron laser facility CLIO in Orsay (France). The spectral dependence of the IR induced fragmentation pattern in the mid-infrared region (800–2000 cm⁻¹) is interpreted with the help of structure and vibrational spectrum calculations of the different protonated conformers. This comparison allows for the assignment of the proton on the terminal amino group, as the most favourable proton site, the neighbouring amide bond being in the trans conformation.

This article presents an automated, model-free, data-driven method for the safe tuning of PID cascade controller gains based on Bayesian optimization. The optimization objective is composed of data-driven performance metrics and modeled using Gaussian processes. The safety requirement is imposed via a barrier-like term in the objective, which is introduced to account for operational changes in the system. We further introduce a data-driven constraint that captures the stability requirements from system data. Numerical evaluation shows that the proposed approach outperforms relay feedback autotuning and quickly converges to the global optimum, thanks to a tailored stopping criterion. We demonstrate the performance of the method through simulations and experiments. For experimental implementation, in addition to the introduced safety constraint, we integrate a method for automatic detection of the critical gains and extend the optimization objective with a penalty depending on the proximity of the current candidate points to the critical gains. The resulting automated tuning method optimizes system performance while ensuring stability and standardization.

In this paper we propose a hierarchical controller for autonomous racing where the same vehicle model is used in a two level optimization framework for motion planning. The high-level controller computes a trajectory that minimizes the lap time, and the low-level nonlinear model predictive path following controller tracks the computed trajectory online. Following a computed optimal trajectory avoids online planning and enables fast computational times. The efficiency is further enhanced by the coupling of the two levels through a terminal constraint, computed in the high-level controller. Including this constraint in the real-time optimization level ensures that the prediction horizon can be shortened, while safety is guaranteed. This proves crucial for the experimental validation of the approach on a full size driverless race car. The vehicle in question won two international student racing competitions using the proposed framework; moreover, our hierarchical controller achieved an improvement of 20% in the lap time compared to the state of the art result achieved using a very similar car and track.