Strong-field quantum control in the extreme ultraviolet domain using pulse shaping.

Tailored light-matter interactions in the strong coupling regime enable the manipulation and control of quantum systems with up to unit efficiency, with applications ranging from quantum information to photochemistry. Although strong light-matter interactions are readily induced at the valence electron level using long-wavelength radiation, comparable phenomena have been only recently observed with short wavelengths, accessing highly excited multi-electron and inner-shell electron states. However, the quantum control of strong-field processes at short wavelengths has not been possible, so far, because of the lack of pulse-shaping technologies in the extreme ultraviolet (XUV) and X-ray domain.

Refining the thermochemical properties of CF, SiF, and their cations by combining photoelectron spectroscopy, quantum chemical calculations, and the Active Thermochemical Tables approach.

Fluorinated species have a pivotal role in semiconductor material chemistry and some of them have been detected beyond the Earth's atmosphere. Achieving good energy accuracy on fluorinated species using quantum chemical calculations has long been a challenge. In addition, obtaining direct experimental thermochemical quantities has also proved difficult.

Solvated dielectrons from optical excitation: An effective source of low-energy electrons.

Low-energy electrons dissolved in liquid ammonia or aqueous media are powerful reducing agents that promote challenging reduction reactions but can also cause radiation damage to biological tissue. Knowledge of the underlying mechanistic processes remains incomplete, particularly with respect to the details and energetics of the electron transfer steps. In this work, we show how ultraviolet (UV) photoexcitation of metal-ammonia clusters could be used to generate tunable low-energy electrons in situ.

Photoionization Dynamics and Proton Transfer within the Adenine-Thymine Nucleobase Pair.

Studying the stability of hydrogen-bonded nucleobase pairs, at the heart of the genetic code, is of utmost importance for an in-depth understanding of basic mechanisms of life and biomolecular evolution. We present here a VUV single photon ionization dynamic study of the nucleobase pair adenine-thymine (AT), revealing its ionization and dissociative ionization thresholds via double imaging electron/ion coincidence spectroscopy. The experimental data, consisting of cluster mass-resolved threshold photoelectron spectra and photon energy-dependent ion kinetic energy release distributions, allow the unambiguous distinction of the dissociation of AT into protonated adenine AH and a dehydrogenated thymine radical T(-H) from dissociative ionization processes of other nucleobase clusters.

Ring-Opening Dynamics of the Cyclopropyl Radical and Cation: the Transition State Nature of the Cyclopropyl Cation.

We provide compelling experimental and theoretical evidence for the transition state nature of the cyclopropyl cation. Synchrotron photoionization spectroscopy employing coincidence techniques together with a novel simulation based on high-accuracy ab initio calculations reveal that the cation is unstable via its allowed disrotatory ring-opening path. The ring strains of the cation and the radical are similar, but both ring opening paths for the radical are forbidden when the full electronic symmetries are considered.

Photoelectron spectroscopy of low valent organophosphorus compounds, P-CH, H-PCH and PCH.

We report the mass-selected slow photoelectron spectra of three reactive organophosphorus species, PCH, and the two isomers, methylenephosphine or phosphaethylene, HPCH and methylphosphinidine, P-CH. All spectra were recorded by double imaging photoelectron-photoion coincidence spectroscopy (iPEPICO) using synchrotron radiation and all species were generated in a flow reactor by the reaction of trimethyl phosphine with fluorine atoms. Adiabatic ionisation energies of 8.

Photoelectron Circular Dichroism as a Signature of Subtle Conformational Changes: The Case of Ring Inversion in 1-Indanol.

Chirality plays a fundamental role in the molecular recognition processes. Molecular flexibility is also crucial in molecular recognition, allowing the interacting molecules to adjust their structures and hence optimize the interaction. Methods probing simultaneously chirality and molecular conformation are therefore crucially needed.

Photoelectron Spectroscopy of the Water Dimer Reveals Unpredicted Vibrational Structure.

Hydrogen bonds and proton transfer reactions can be considered as being at the very heart of aqueous chemistry and of utmost importance for many processes of biological relevance. Nevertheless, these processes are not yet well understood, even in seemingly simple model systems like small water clusters. We present a study of the photoelectron spectrum of the water dimer, revealing previously unresolved vibrational structure with 10-30 meV (80-242 cm) typical splitting, in disagreement with a previous theoretical photoionization study predicting an apparent main vibrational progression with an ∼130 meV spacing [Kamarchik et al.

Low-energy constraints on photoelectron spectra measured from liquid water and aqueous solutions.

We report on the effects of electron collision and indirect ionization processes, occurring at photoexcitation and electron kinetic energies well below 30 eV, on the photoemission spectra of liquid water. We show that the nascent photoelectron spectrum and, hence, the inferred electron binding energy can only be accurately determined if electron energies are large enough that cross sections for quasi-elastic scattering processes, such as vibrational excitation, are negligible. Otherwise, quasi-elastic scattering leads to strong, down-to-few-meV kinetic energy scattering losses from the direct photoelectron features, which manifest in severely distorted intrinsic photoelectron peak shapes.

Condensation Effects on Electron Chiral Asymmetries in the Photoionization of Serine: From Free Molecules to Nanoparticles.

Structural changes at the molecular level, occurring at the onset of condensation, can be probed by angle-resolved valence photoelectron spectroscopy, which is inherently sensitive to the electronic structure. For larger condensed systems like aerosol particles, the observation of intrinsic angular anisotropies in photoemission (β parameters) is challenging due to the strong reduction of their magnitude by electron transport effects. Here, we use a less common, more sensitive observable in the form of the chiral asymmetry parameter to perform a comparative study of the VUV photoelectron spectroscopy and photoelectron circular dichroism (PECD) between pure gas phase enantiomers of the amino acid serine and their corresponding homochiral nanoparticles.

VUV photoionization of the CHNC radical: adiabatic ionization energy and cationic vibrational mode wavenumber determinations.

The photoelectron spectroscopy of CHNC (isocyanomethyl) radical species is investigated for the first time between 9.3 and 11.2 eV in the vicinity of the first photoionizing transition XA← X B.

Relaxation Dynamics and Genuine Properties of the Solvated Electron in Neutral Water Clusters.

We have investigated the solvation dynamics and the genuine binding energy and photoemission anisotropy of the solvated electron in neutral water clusters with a combination of time-resolved photoelectron velocity map imaging and electron scattering simulations. The dynamics was probed with a UV probe pulse following above-band-gap excitation by an EUV pump pulse. The solvation dynamics is completed within about 2 ps.

Electron scattering in large water clusters from photoelectron imaging with high harmonic radiation.

Low-energy electron scattering in water clusters (H2O)n with average cluster sizes of n < 700 is investigated by angle-resolved photoelectron spectroscopy using high harmonic radiation at photon energies of 14.0, 20.3, and 26.

Size-Resolved Photoelectron Anisotropy of Gas Phase Water Clusters and Predictions for Liquid Water.

We report the first measurements of size-resolved photoelectron angular distributions for the valence orbitals of neutral water clusters with up to 20 molecules. A systematic decrease of the photoelectron anisotropy is found for clusters with up to 5-6 molecules, and most remarkably, convergence of the anisotropy for larger clusters. We suggest the latter to be the result of a local short-range scattering potential that is fully described by a unit of 5-6 molecules.

Metal Transition in Sodium-Ammonia Nanodroplets.

The famous nonmetal-to-metal transition in Na-ammonia solutions is investigated in nanoscale solution droplets by photoelectron spectroscopy. In agreement with the bulk solutions, a strong indication for a transition to the metallic state is found at an average metal concentration of 8.8±2.

Stability of aerosol droplets in Bessel beam optical traps under constant and pulsed external forces.

We report on the dynamics of aerosol droplets in optical traps under the influence of additional constant and pulsed external forces. Experimental results are compared with simulations of the three-dimensional droplet dynamics for two types of optical traps, the counter-propagating Bessel beam (CPBB) trap and the quadruple Bessel beam (QBB) trap. Under the influence of a constant gas flow (constant external force), the QBB trap is found to be more stable compared with the CPBB trap.