Fragmentation of water clusters formed in helium nanodroplets by charge transfer and Penning ionization.

Helium nanodroplets ("HNDs") are widely used for forming tailor-made clusters and molecular complexes in a cold, transparent, and weakly interacting matrix. The characterization of embedded species by mass spectrometry is often complicated by the fragmentation and trapping of ions in the HNDs. Here, we systematically study fragment ion mass spectra of HND-aggregated water and oxygen clusters following their ionization by charge transfer ionization ("CTI") and Penning ionization ("PEI"). While the efficiency of PEI of embedded clusters is lower than for CTI by about factor 10, both the mean sizes of detected water clusters and the relative yields of unprotonated cluster ions are significantly larger, making PEI a "soft ionization" scheme. However, the tendency of ions to remain bound to HNDs leads to a reduced detection efficiency for large HNDs containing >104 helium atoms. These results are instrumental in determining optimal conditions for mass spectrometry and photoionization spectroscopy of molecular complexes and clusters aggregated in HNDs.

Method of kinetic energy reconstruction from time-of-flight mass spectra.

We present a method for the reconstruction of ion kinetic energy distributions from ion time-of-flight mass spectra through ion trajectory simulations. In particular, this method is applicable to complicated spectrometer geometries with largely anisotropic ion collection efficiencies. A calibration procedure using a single ion mass peak allows the accurate determination of parameters related to the spectrometer calibration, experimental alignment, and instrument response function, which improves the agreement between simulations and experiment. The calibrated simulation is used to generate a set of basis functions for the time-of-flight spectra, which are then used to transform from time-of-flight to kinetic-energy spectra. We demonstrate this reconstruction method on a recent pump-probe experiment by Asmussen et al. [Asmussen et al., Phys. Chem. Chem. Phys., 23, 15138, (2021)] on helium nanodroplets and retrieve time-resolved kinetic-energy-release spectra for the ions from ion time-of-flight spectra.

Efficient Indirect Interatomic Coulombic Decay Induced by Photoelectron Impact Excitation in Large Pure Helium Nanodroplets.

Ionization of matter by energetic radiation generally causes complex secondary reactions that are hard to decipher. Using large helium nanodroplets irradiated by extreme ultraviolet (XUV) photons, we show that the full chain of processes ensuing primary photoionization can be tracked in detail by means of high-resolution electron spectroscopy. We find that elastic and inelastic scattering of photoelectrons efficiently induces interatomic Coulombic decay (ICD) in the droplets. This type of indirect ICD even becomes the dominant process of electron emission in nearly the entire XUV range in large droplets with radius ≳40 nm. Indirect ICD processes induced by electron scattering likely play an important role in other condensed-phase systems exposed to ionizing radiation as well, including biological matter.

Relaxation dynamics in excited helium nanodroplets probed with high resolution, time-resolved photoelectron spectroscopy.

Superfluid helium nanodroplets are often considered as transparent and chemically inert nanometer-sized cryo-matrices for high-resolution or time-resolved spectroscopy of embedded molecules and clusters. On the other hand, when the helium nanodroplets are resonantly excited with XUV radiation, a multitude of ultrafast processes are initiated, such as relaxation into metastable states, formation of nanoscopic bubbles or excimers, and autoionization channels generating low-energy free electrons. Here, we discuss the full spectrum of ultrafast relaxation processes observed when helium nanodroplets are electronically excited. In particular, we perform an in-depth study of the relaxation dynamics occurring in the lowest 1s2s and 1s2p droplet bands using high resolution, time-resolved photoelectron spectroscopy. The simplified excitation scheme and improved resolution allow us to identify the relaxation into metastable triplet and excimer states even when exciting below the droplets' autoionization threshold, unobserved in previous studies.

Fragmentation dynamics of doubly charged camphor molecule following C 1s Auger decay.

The fragmentation dynamics of the gas-phase, doubly charged camphor molecule, formed by Auger decay following carbon 1s ionisation, using soft X-ray synchrotron radiation, is presented in this work. The technique of velocity map imaging combined with a photoelectron-photoion-photoion coincidence (VMI-PEPIPICO) is used for both electron energy and ion momentum (in-sequence) measurements. The experimental study is complemented by molecular dynamics simulation, performed with an NVT (moles, volume, and temperature) ensemble. Velocity Verlet algorithms were used for time integration at various internal energies. These simulations validate observed dissociation pathways. From these, we successfully deduce that the internal energy of the doubly charged molecular ion has a significant contribution to the fragmentation mechanism. Notably, a prominent signature of the internal energy was observed in the experimentally determined energies of the neutral fragment in these deferred charge separation pathways, entailing a more detailed theoretical study to uncover the exact dissociation dynamics.

Enhancement of Above Threshold Ionization in Resonantly Excited Helium Nanodroplets.

Clusters and nanodroplets hold the promise of enhancing high-order nonlinear optical effects due to their high local density. However, only moderate enhancement has been demonstrated to date. Here, we report the observation of energetic electrons generated by above-threshold ionization (ATI) of helium (He) nanodroplets which are resonantly excited by ultrashort extreme ultraviolet (XUV) free-electron laser pulses and subsequently ionized by near-infrared (NIR) or near-ultraviolet (UV) pulses. The electron emission due to high-order ATI is enhanced by several orders of magnitude compared with He atoms. The crucial dependence of the ATI intensities with the number of excitations in the droplets suggests a local collective enhancement effect.

Coincident angle-resolved state-selective photoelectron spectroscopy of acetylene molecules: a candidate system for time-resolved dynamics.

The acetylene-vinylidene system serves as a benchmark for investigations of ultrafast dynamical processes where the coupling of the electronic and nuclear degrees of freedom provides a fertile playground to explore the femto- and sub-femto-second physics with coherent extreme-ultraviolet (EUV) photon sources both on the table-top as well as free-electron lasers. We focus on detailed investigations of this molecular system in the photon energy range 19-40 eV where EUV pulses can probe the dynamics effectively. We employ photoelectron-photoion coincidence (PEPICO) spectroscopy to uncover hitherto unrevealed aspects of this system. In this work, the role of excited states of the C2H2+ cation, the primary photoion, is specifically addressed. From photoelectron energy spectra and angular distributions, the nature of the dissociation and isomerization channels is discerned. Exploiting the 4π-collection geometry of the velocity map imaging spectrometer, we not only probe pathways where the efficiency of photoionization is inherently high but also perform PEPICO spectroscopy on relatively weak channels.

Penning spectroscopy and structure of acetylene oligomers in He nanodroplets.

Embedded atoms or molecules in a photoexcited He nanodroplet are well-known to be ionized through inter-atomic relaxation in a Penning process. In this work, we investigate the Penning ionization of acetylene oligomers occurring from the photoexcitation bands of He nanodroplets. In close analogy to conventional Penning electron spectroscopy by thermal atomic collisions, the n = 2 photoexcitation band plays the role of the metastable atomic 1s2s 3,1S He*. This facilitates electron spectroscopy of acetylene aggregates in the sub-Kelvin He environment, providing the following insight into their structure: the molecules in the dopant cluster are loosely bound van der Waals complexes rather than forming covalent compounds. In addition, this work reveals a Penning process stemming from the n = 4 band where charge-transfer from autoionized He in the droplets is known to be the dominant relaxation channel. This allows for excited states of the remnant dopant oligomer Penning-ions to be studied. Hence, we demonstrate Penning ionization electron spectroscopy of doped droplets as an effective technique for investigating dopant oligomers which are easily formed by attachment to the host cluster.

Electron transfer mediated decay of alkali dimers attached to He nanodroplets.

Alkali metal dimers attached to the surface of helium nanodroplets are found to be efficiently doubly ionized by electron transfer mediated decay (ETMD) when photoionizing the helium droplets. This process is evidenced by detecting in coincidence two energetic ions created by Coulomb explosion and one low-kinetic energy electron. The kinetic energy spectra of ions and electrons are reproduced by simple model calculations based on diatomic potential energy curves, and are in agreement with ab initio calculations for the He-Na2 and He-KRb systems. This work demonstrates that ETMD is an important decay channel in heterogeneous nanosystems exposed to ionizing radiation.

Ultrafast relaxation of photoexcited superfluid He nanodroplets.

The relaxation of photoexcited nanosystems is a fundamental process of light-matter interaction. Depending on the couplings of the internal degrees of freedom, relaxation can be ultrafast, converting electronic energy in a few fs, or slow, if the energy is trapped in a metastable state that decouples from its environment. Here, we study helium nanodroplets excited resonantly by femtosecond extreme-ultraviolet (XUV) pulses from a seeded free-electron laser. Despite their superfluid nature, we find that helium nanodroplets in the lowest electronically excited states undergo ultrafast relaxation. By comparing experimental photoelectron spectra with time-dependent density functional theory simulations, we unravel the full relaxation pathway: Following an ultrafast interband transition, a void nanometer-sized bubble forms around the localized excitation (He[Formula: see text]) within 1 ps. Subsequently, the bubble collapses and releases metastable He[Formula: see text] at the droplet surface. This study highlights the high level of detail achievable in probing the photodynamics of nanosystems using tunable XUV pulses.

Charge Exchange Dominates Long-Range Interatomic Coulombic Decay of Excited Metal-Doped Helium Nanodroplets.

Atoms and molecules attached to rare-gas clusters are ionized by an interatomic autoionization process traditionally termed "Penning ionization" when the host cluster is resonantly excited. Here we analyze this process in the light of the interatomic Coulombic decay (ICD) mechanism, which usually contains a contribution from charge exchange at a short interatomic distance and one from virtual photon transfer at a large interatomic distance. For helium (He) nanodroplets doped with alkali metal atoms (Li, Rb), we show that long-range and short-range contributions to the interatomic autoionization can be clearly distinguished by detecting electrons and ions in coincidence. Surprisingly, ab initio calculations show that even for alkali metal atoms floating in dimples at a large distance from the nanodroplet surface, autoionization is largely dominated by charge-exchange ICD. Furthermore, the measured electron spectra manifest the ultrafast internal relaxation of the droplet mainly into the 1s2s1S state and partially into the metastable 1s2s3S state.

Real-Time Dynamics of the Formation of Hydrated Electrons upon Irradiation of Water Clusters with Extreme Ultraviolet Light.

Free electrons in a polar liquid can form a bound state via interaction with the molecular environment. This so-called hydrated electron state in water is of fundamental importance, e.g., in cellular biology or radiation chemistry. Hydrated electrons are highly reactive radicals that can either directly interact with DNA or enzymes, or form highly excited hydrogen (H^{*}) after being captured by protons. Here, we investigate the formation of the hydrated electron in real-time employing extreme ultraviolet femtosecond pulses from a free electron laser, in this way observing the initial steps of the hydration process. Using time-resolved photoelectron spectroscopy we find formation timescales in the low picosecond range and resolve the prominent dynamics of forming excited hydrogen states.

Inelastic scattering of photoelectrons from He nanodroplets.

We present a detailed study of inelastic energy-loss collisions of photoelectrons emitted from He nanodroplets by tunable extreme ultraviolet (XUV) radiation. Using coincidence imaging detection of electrons and ions, we probe the lowest He droplet excited states up to the electron impact ionization threshold. We find significant signal contributions from photoelectrons emitted from free He atoms accompanying the He nanodroplet beam. Furthermore, signal contributions from photoionization and electron impact excitation/ionization occurring in pairs of nearest-neighbor atoms in the He droplets are detected. This work highlights the importance of inelastic electron scattering in the interaction of nanoparticles with XUV radiation.

Penning Ionization of Acene Molecules by Helium Nanodroplets.

Acene molecules (anthracene, tetracene, pentacene) and fullerene (C60) are embedded in He nanodroplets (HeN) and probed by EUV synchrotron radiation. When resonantly exciting the He nanodroplets, the embedded molecules M are efficiently ionized by the Penning reaction HeN* + M → HeN + M+ + e-. However, the Penning electron spectra are all broad and structureless, largely differing from those measured by binary Penning collisions, as well as from those measured for dopants bound to the He droplet surface. Simulations based on elastic binary electron-He collisions qualitatively reproduce the measured spectra only when assuming unexpectedly large He droplets, indicating that electron spectra of molecules embedded in helium nanodroplets are severely affected by collective electron-helium interactions.

A compact design for velocity-map imaging of energetic electrons and ions.

We present a compact design for a velocity-map imaging spectrometer for energetic electrons and ions. The standard geometry by Eppink and Parker [Rev. Sci. Instrum. 68, 3477 (1997)] is augmented by just two extended electrodes so as to realize an additional einzel lens. In this way, for a maximum electrode voltage of 7 kV, we experimentally demonstrate imaging of electrons with energies up to 65 eV. Simulations show that energy acceptances ≲270 and ≲1200 eV with an energy resolution ΔE∕E≲5% are achievable for electrode voltages ≤20 kV when using diameters of the position-sensitive detector of 42 and 78 mm, respectively.

Time-Resolved Measurement of Interatomic Coulombic Decay Induced by Two-Photon Double Excitation of Ne_{2}.

The hitherto unexplored two-photon doubly excited states [Ne^{*}(2p^{-1}3s)]_{2} were experimentally identified using the seeded, fully coherent, intense extreme ultraviolet free-electron laser FERMI. These states undergo ultrafast interatomic Coulombic decay (ICD), which predominantly produces singly ionized dimers. In order to obtain the rate of ICD, the resulting yield of Ne_{2}^{+} ions was recorded as a function of delay between the extreme ultraviolet pump and UV probe laser pulses. The extracted lifetimes of the long-lived doubly excited states, 390(-130/+450) fs, and of the short-lived ones, less than 150 fs, are in good agreement with ab initio quantum mechanical calculations.

A simple photoionization scheme for characterizing electron and ion spectrometers.

We present a simple diode laser-based photoionization scheme for generating electrons and ions with well-defined spatial and energetic (≲2 eV) structures. This scheme can easily be implemented in ion or electron imaging spectrometers for the purpose of off-line characterization and calibration. The low laser power ∼1 mW needed from a passively stabilized diode laser and the low flux of potassium atoms in an effusive beam make our scheme a versatile source of ions and electrons for applications in research and education.

Desorption Dynamics of Rb2 Molecules Off the Surface of Helium Nanodroplets.

The desorption dynamics of rubidium dimers (Rb2) off the surface of helium nanodroplets induced by laser excitation is studied by employing both nanosecond and femtosecond ion imaging spectroscopy. Similarly to alkali metal atoms, we find that the Rb2 desorption process resembles the dissociation of a diatomic molecule. However, both angular and energy distributions of detected Rb2+ ions appear to be most crucially determined by the Rb2 intramolecular degrees of freedom rather than by those of the Rb2HeN complex. The pump-probe dynamics of Rb2+ is found to be slower than that of Rb+, pointing at a weaker effective guest-host repulsion for excited molecules than for single atoms.

Role of ion-pair states in the predissociation dynamics of Rydberg states of molecular iodine.

Using femtosecond pump-probe ion imaging spectroscopy, we establish the key role of I(+) + I(-) ion-pair (IP) states in the predissociation dynamics of molecular iodine I2 excited to Rydberg states. Two-photon excitation of Rydberg states lying above the lowest IP state dissociation threshold (1st tier) is found to be followed by direct parallel transitions into IP states of the 1st tier asymptotically correlating to a pair of I ions in their lowest states I(+)((3)P2) + I(-)((1)S0), of the 2nd tier correlating to I(+)((3)P0) + I(-)((1)S0), and of the 3rd tier correlating to I(+)((1)D2) + I(-)((1)S0). Predissociation via the 1st tier proceeds presumably with a delay of 1.6-1.7 ps which is close to the vibrational period in the 3rd tier state (3rd tier-mediated process). The 2nd tier IP state is concluded to be the main precursor for predissociation via lower lying Rydberg states proceeding with a characteristic time of 7-8 ps and giving rise to Rydberg atoms I(5s(2)5p(4)6s(1)). The channel generating I((2)P3/2) + I((2)P1/2) atoms with total kinetic energy corresponding to one-photon excitation is found to proceed via a pump - dump mechanism with dramatic change of angular anisotropy of this channel as compared with earlier nanosecond experiments.

Enhanced Ionization of Embedded Clusters by Electron-Transfer-Mediated Decay in Helium Nanodroplets.

We report the observation of electron-transfer-mediated decay (ETMD) involving magnesium (Mg) clusters embedded in helium (He) nanodroplets. ETMD is initiated by the ionization of He followed by removal of two electrons from the Mg clusters of which one is transferred to the He ion while the other electron is emitted into the continuum. The process is shown to be the dominant ionization mechanism for embedded clusters for photon energies above the ionization potential of He. For Mg clusters larger than five atoms we observe stable doubly ionized clusters. Thus, ETMD provides an efficient pathway to the formation of doubly ionized cold species in doped nanodroplets.