Comment on "Terahertz pump-probe of liquid water at 12.3 THz" by F. Novelli, C. Hoberg, E. M. Adams, J. M. Klopf and M. Havenith, Phys. Chem. Chem. Phys., 2022, 24, 653-665.

The interpretation of the data presented by Novelli at al. as the nonlinear response of water is questioned.

Magnetoquantum Oscillations at THz Frequencies in InSb.

The ac magnetoconductance of bulk InSb at THz frequencies in high magnetic fields, as measured by the transmission of THz radiation, shows a field-induced transmission, which at high temperatures (≈100 K) is well explained with classical magnetoplasma effects (helicon waves). However, at low temperatures (4 K), the transmitted radiation intensity shows magnetoquantum oscillations that represent the Shubnikov-de Haas effect at THz frequencies. At frequencies above 0.9 THz, when the radiation period is shorter than the Drude scattering time, an anomalously high transmission is observed in the magnetic quantum limit that can be interpreted as carrier localization at high frequencies.

Coherent control of Rydberg states in silicon.

Laser cooling and electromagnetic traps have led to a revolution in atomic physics, yielding dramatic discoveries ranging from Bose-Einstein condensation to the quantum control of single atoms. Of particular interest, because they can be used in the quantum control of one atom by another, are excited Rydberg states, where wavefunctions are expanded from their ground-state extents of less than 0.1 nm to several nanometres and even beyond; this allows atoms far enough apart to be non-interacting in their ground states to strongly interact in their excited states. For eventual application of such states, a solid-state implementation is very desirable. Here we demonstrate the coherent control of impurity wavefunctions in the most ubiquitous donor in a semiconductor, namely phosphorus-doped silicon. In our experiments, we use a free-electron laser to stimulate and observe photon echoes, the orbital analogue of the Hahn spin echo, and Rabi oscillations familiar from magnetic resonance spectroscopy. As well as extending atomic physicists' explorations of quantum phenomena to the solid state, our work adds coherent terahertz radiation, as a particularly precise regulator of orbitals in solids, to the list of controls, such as pressure and chemical composition, already familiar to materials scientists.

Single-size thermometric measurements on a size distribution of neutral fullerenes.

We present measurements of the velocity distribution of electrons emitted from mass-selected neutral fullerenes, performed at the intracavity free electron laser FELICE. We make use of mass-specific vibrational resonances in the infrared domain to selectively heat up one out of a distribution of several fullerene species. Efficient energy redistribution leads to decay via thermionic emission. Time-resolved electron kinetic energy distributions measured give information on the decay rate of the selected fullerene. This method is generally applicable to all neutral species that exhibit thermionic emission and provides a unique tool to study the stability of mass-selected neutral clusters and molecules that are only available as part of a size distribution.

Structures of the dehydrogenation products of methane activation by 5d transition metal cations.

The activation of methane by gas-phase transition metal cations (M(+)) has been studied extensively, both experimentally and using density functional theory (DFT). Methane is exothermically dehydrogenated by several 5d metal ions to form [M,C,2H](+) and H2. However, the structure of the dehydrogenation product has not been established unambiguously. Two types of structures have been considered: a carbene structure where an intact CH2 fragment is bound to the metal (M(+)-CH2) and a carbyne (hydrido-methylidyne) structure with both a CH and a hydrogen bound to the metal separately (H-M(+)-CH). For metal ions with empty d-orbitals, an agostic interaction can occur that could influence the competition between carbene and carbyne structures. In this work, the gas phase [M,C,2H](+) (M = Ta, W, Ir, Pt) products are investigated by infrared multiple-photon dissociation (IR-MPD) spectroscopy using the Free-Electron Laser for IntraCavity Experiments (FELICE). Metal cations are formed in a laser ablation source and react with methane pulsed into a reaction channel downstream. IR-MPD spectra of the [M,C,2H](+) species are measured in the 300-3500 cm(-1) spectral range by monitoring the loss of H (2H in the case of [Ir,C,2H](+)). For each system, the experimental spectrum closely resembles the calculated spectrum of the lowest energy structure calculated using DFT: for Pt, a classic C(2v) carbene structure; for Ta and W, carbene structures that are distorted by agostic interactions; and a carbyne structure for the Ir complex. The Ir carbyne structure was not considered previously. To obtain this agreement, the calculated harmonic frequencies are scaled with a scaling factor of 0.939, which is fairly low and can be attributed to the strong redshift induced by the IR multiple-photon excitation process of these small molecules. These four-atomic species are among the smallest systems studied by IR-FEL based IR-MPD spectroscopy, and their spectra demonstrate the power of IR spectroscopy in resolving long-standing chemical questions.

Scaling laws for photoelectron holography in the midinfrared wavelength regime.

Midinfrared strong-field laser ionization offers the promise of measuring holograms of atoms and molecules, which contain both spatial and temporal information of the ion and the photoelectron with subfemtosecond temporal and angstrom spatial resolution. We report on the scaling of photoelectron holographic interference patterns with the laser pulse duration, wavelength, and intensity. High-resolution holograms for the ionization of metastable xenon atoms by 7-16 µm light from the FELICE free electron laser are presented and compared to semiclassical calculations that provide analytical insight.

Acid solvation versus dissociation at "stardust conditions": Reaction sequence matters.

Chemical reactions at ultralow temperatures are of fundamental importance to primordial molecular evolution as it occurs on icy mantles of dust nanoparticles or on ultracold water clusters in dense interstellar clouds. As we show, studying reactions in a stepwise manner in ultracold helium nanodroplets by mass-selective infrared (IR) spectroscopy provides an avenue to mimic these "stardust conditions" in the laboratory. In our joint experimental/theoretical study, in which we successively add H2O molecules to HCl, we disclose a unique IR fingerprint at 1337 cm-1 that heralds hydronium (H3O+) formation and, thus, acid dissociation generating solvated protons. In stark contrast, no reaction is observed when reversing the sequence by allowing HCl to interact with preformed small embryonic ice-like clusters. Our ab initio simulations demonstrate that not only reaction stoichiometry but also the reaction sequence needs to be explicitly considered to rationalize ultracold chemistry.

Spin preservation during THz orbital pumping of shallow donors in silicon.

We investigate the spin relaxation under conditions of optical excitation between the Rydberg orbital states of phosphorus donor impurities in silicon. Here we show that the spin relaxation is less than a few percent, even after multiple excitation/relaxation cycles. The observed high level of spin preservation may be useful for readout cycling or in quantum information schemes where coupling of neighbor qubits is via orbital excitation.

Coherent creation and destruction of orbital wavepackets in Si:P with electrical and optical read-out.

The ability to control dynamics of quantum states by optical interference, and subsequent electrical read-out, is crucial for solid state quantum technologies. Ramsey interference has been successfully observed for spins in silicon and nitrogen vacancy centres in diamond, and for orbital motion in InAs quantum dots. Here we demonstrate terahertz optical excitation, manipulation and destruction via Ramsey interference of orbital wavepackets in Si:P with electrical read-out. We show milliradian control over the wavefunction phase for the two-level system formed by the 1s and 2p states. The results have been verified by all-optical echo detection methods, sensitive only to coherent excitations in the sample. The experiments open a route to exploitation of donors in silicon for atom trap physics, with concomitant potential for quantum computing schemes, which rely on orbital superpositions to, for example, gate the magnetic exchange interactions between impurities.

Time-resolved holography with photoelectrons.

Ionization is the dominant response of atoms and molecules to intense laser fields and is at the basis of several important techniques, such as the generation of attosecond pulses that allow the measurement of electron motion in real time. We present experiments in which metastable xenon atoms were ionized with intense 7-micrometer laser pulses from a free-electron laser. Holographic structures were observed that record underlying electron dynamics on a sublaser-cycle time scale, enabling photoelectron spectroscopy with a time resolution of almost two orders of magnitude higher than the duration of the ionizing pulse.

Benchmarking of electro-optic monitors for femtosecond electron bunches.

The longitudinal profiles of ultrashort relativistic electron bunches at the soft x-ray free-electron laser FLASH have been investigated using two single-shot detection schemes: an electro-optic (EO) detector measuring the Coulomb field of the bunch and a radio-frequency structure transforming the charge distribution into a transverse streak. A comparison permits an absolute calibration of the EO technique. EO signals as short as 60 fs (rms) have been observed, which is a new record in the EO detection of single electron bunches and close to the limit given by the EO material properties.

Spin relaxation by transient monopolar and bipolar optical orientation.

We have used two-color time-resolved spectroscopy to measure the relaxation of electron spin polarizations in a bulk semiconductor. The circularly polarized pump beam induces a polarization either by direct excitation from the valence band, or by free-carrier (Drude) absorption when tuned to an energy below the band gap. We find that the spin relaxation time, measured with picosecond time resolution by resonant induced Faraday rotation in both cases, increases in the presence of photogenerated holes. In the case of the material chosen, n-InSb, the increase was from 14 to 38 ps.

Electro-optic technique with improved time resolution for real-time, nondestructive, single-shot measurements of femtosecond electron bunch profiles.

Electro-optic detection of the Coulomb field of a relativistic electron bunch combined with single-shot cross correlation of optical pulses is used to enable single-shot measurements of the shape and length of femtosecond electron bunches. This method overcomes a fundamental time-resolution limit of previous single-shot electro-optic measurements, which arises from the inseparability of time and frequency properties of the probing optical pulse. Using this new technique we have made real-time measurements of a 50 MeV electron bunch, observing the profile of 650 fs FWHM ( approximately 275 fs rms) long bunches.

Single-shot electron-beam bunch length measurements.

We report subpicosecond electro-optic measurements of the length of individual relativistic electron bunches. The longitudinal electron-bunch shape is encoded electro-optically on to the spectrum of a chirped laser pulse. The electron-bunch length is determined by analyzing individual laser-pulse spectra obtained with and without the presence of an electron bunch. Since the length of the chirped laser pulse can be easily changed, the electron bunch can be visualized on different time scales. This single-shot imaging technique is a promising method for real-time electron-bunch diagnostics.