Valence photoelectron imaging of molecular oxybenzone.

An oxybenzone molecule in the gas phase was characterized by mass spectrometry and angle-resolved photoelectron spectroscopy, using both single and multiphoton ionization schemes. A tabletop high harmonic generation source with a monochromator was used for single-photon ionization of oxybenzone with photon energies of up to 35.7 eV. From this, vertical ionization and appearance energies, as well as energy-dependent anisotropy parameters were retrieved and compared with the results from DFT calculations. For two-photon ionization using 4.7 eV light, we found a higher appearance energy than in the extreme ultraviolet (EUV) case, highlighting the possible influence of an intermediate state on the photoionization process. We found no differences in the mass spectra when ionizing oxybenzone by single-photons between 17.2 and 35.7 eV. However, for the multiphoton ionization, the fragmentation process was found to be sensitive to the photoionization order and laser intensity. The "softest" method was found to be two-photon ionization using 4.7 eV light, which led to no measurable fragmentation up to an intensity of 5 × 1012 W cm-2.

Ion imaging of spatially inhomogeneous nanoplasmas in NaCl particles.

Studying photoemission from free, unsupported aerosol particles is a powerful method for gaining insight into light-matter interactions at the nanoscale. We used single-shot velocity map imaging to experimentally measure kinetic energy and angular distributions of ions emitted following interaction of sub-micrometer NaCl particles with femtosecond pulses of near infrared (NIR, 800 nm) and ultraviolet (UV, 266 nm) light. We combined this with time-dependent simulations of light propagation through the particles and a rate equation approach to computationally address the origin of the observed ion emission. For both NIR and UV pulses, ion emission is caused by the formation of an under-dense nanoplasma with similar densities, although using an order of magnitude weaker UV intensities. Such conditions result in remarkably similar ion fragments with similar kinetic energies, and no obvious influence of the plasma formation mechanism (photoionization or collisional ionization). Our data suggests that Coulomb explosion does not play a significant role for ion emission, and we discuss alternative mechanisms that can lead to material ablation from under-dense nanoplasma. Finally, we show how finite size effects play an important role in photoemission through generation of spatially inhomogeneous nanoplasmas, which result in asymmetric ion emission that depends on particle size and laser wavelength. By utilizing the single-particle information available from our experiments, we show how finite size effects and inhomogeneous nanoplasma formation can be exploited to retrieve the size and orientation of individual submicrometer aerosol particles.

Comparison of Magnetic Deflection among Neutral Sodium-Doped Clusters: Na(H2O)n, Na(NH3)n, Na(MeOH)n, and Na(DME)n.

Using a pulsed Stern-Gerlach deflection experiment, we present the results of a comparative study on the magnetic properties of neutral sodium-doped solvent clusters Na(Sol)n with n = 1-4 (Sol: H2O, NH3, CH3OH, CH3OCH3). Experimental deflection ratios are compared with values calculated from molecular dynamics simulations. NaNH3 and NaH2O are deflected as a spin 1/2 system, consistent with spin transitions occurring on a time scale significantly longer than 100 µs. For all other clusters, reduced deflection is observed. The observed magnetic deflection behavior is correlated to the number of thermally populated rotational states in the clusters. We discuss that spin-rotational couplings allow for avoided crossings and a reduction in the effective magnetic moment of the cluster. This work attempts to understand the evolution of magnetic properties in isolated weakly bound clusters and is relevant to diamagnetic and paramagnetic species expected to exist in solvated electron systems.

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. Specifically, we identified UV light-induced generation of spin-paired solvated dielectrons and their subsequent relaxation by an unconventional electron transfer-mediated decay as an efficient, low-energy electron source. The process is robust and straightforward to induce with the prospect of improving our understanding of radiation damage and fostering mechanistic studies of solvated electron reduction reactions.

Time-dependent photoemission from droplets: influence of size and charge on the photophysics near the surface.

Photoemission from submicrometer droplets containing a mixture of dioctyl phthalate and dioctyl sebacate was investigated by femtosecond and nanosecond photoionization. Photoelectron spectra recorded after ionization with single 4.7 eV femtosecond or nanosecond laser pulses showed marked differences between the two cases. These differences were attributed to ionization of long-lived states which only occurred within the duration of the nanosecond pulse. The tentative assignment of the long-lived states to dioctyl phthalate triplet states is discussed. A nanosecond-femtosecond pump-probe scheme using 4.7 eV (pump) and 3.1 eV (probe) pulses was used to investigate the decay dynamics of these long-lived states. The dynamics showed an accelerated decay rate at higher dioctyl phthalate concentrations. Furthermore, the dependence of the decay dynamics on droplet size and charge was investigated. The decay of the long-lived states was found to be faster in smaller droplets as well as in neutral droplets compared with both positively and negatively charged droplets. Possible mechanisms to explain these observations and the dominance of contributions from the droplets surface are discussed.

Size-Resolved Electron Solvation in Neutral Water Clusters.

Cluster-size-resolved ultrafast dynamics of the solvated electron in neutral water clusters with n = 3 to ∼200 molecules are studied with pump-probe time-of-flight mass spectrometry after below band gap excitation. For the smallest clusters, no longer-lived (>100-200 fs) hydrated electrons were detected, indicating a minimum size of n ∼ 14 for being able to sustain hydrated electrons. Larger clusters show a systematic increase of the number of hydrated electrons per molecule on the femtosecond to picosecond time scale. We propose that with increasing cluster size the underlying dynamics is governed by more effective electron formation processes combined with less effective electron loss processes, such as ultrafast hydrogen ejection and recombination. It appears unlikely that any size dependence of the solvent relaxation dynamics would be reflected in the observed time-resolved ion yields.

Below Band Gap Formation of Solvated Electrons in Neutral Water Clusters?

Below band gap formation of solvated electrons in neutral water clusters using pump-probe photoelectron imaging is compared with recent data for liquid water and with above band gap excitation studies in liquid and clusters. Similar relaxation times on the order of 200 fs and 1-2 ps are retrieved for below and above band gap excitation, in both clusters and liquid. The independence of the relaxation times from the generation process indicates that these times are dominated by the solvent response, which is significantly slower than the various solvated electron formation processes. The analysis of the temporal evolution of the vertical electron binding energy and the electron binding energy at half-maximum suggests a dependence of the solvation time on the binding energy.

Photoemission from Free Particles and Droplets.

Intriguing properties of photoemission from free, unsupported particles and droplets were predicted nearly 50 years ago, though experiments were a technical challenge. The last few decades have seen a surge of research in the field, due to advances in aerosol technology (generation, characterization, and transfer into vacuum), the development of photoelectron imaging spectrometers, and advances in vacuum ultraviolet and ultrafast light sources. Particles and droplets offer several advantages for photoemission studies. For example, photoemission spectra are dependent on the particle's size, shape, and composition, providing a wealth of information that allows for the retrieval of genuine electronic properties of condensed phase. In this review, with a focus on submicrometer-sized, dielectric particles and droplets, we explain the utility of photoemission from such systems, summarize several applications from the literature, and present some thoughts on future research directions.

Low-Energy Electron Escape from Liquid Interfaces: Charge and Quantum Effects.

The high surface sensitivity and controlled surface charge state of submicron sized droplets is exploited to study low-energy electron transport through liquid interfaces using photoelectron imaging. Already a few charges on a droplet are found to modify the photoelectron images significantly. For narrow escape barriers, the comparison with an electron scattering model reveals pronounced quantum effects in the form of above-barrier reflections at electron kinetic energies below about 1 eV. The observed susceptibility to the characteristics of the electron escape barrier might provide access to these properties for liquid interfaces, which are generally difficult to investigate.

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. Only a single band is observed in the spectra, with no indication for isomers with distinct binding energies. Data analysis with an electron scattering model reveals a genuine binding energy in the range of 3.55-3.85 eV and a genuine anisotropy parameter in the range of 0.51-0.66 for the ground-state hydrated electron. All of these observations coincide with those for liquid bulk, which is rather unexpected for an average cluster size of 300 molecules.

Magic Numbers for the Photoelectron Anisotropy in Li-Doped Dimethyl Ether Clusters.

Photoelectron velocity map imaging of Li(CH3OCH3) n clusters (1 ≤ n ≤ 175) is used to search for magic numbers related to the photoelectron anisotropy. Comparison with density functional calculations reveals magic numbers at n = 4, 5, and 6, resulting from the symmetric charge distribution with high s-character of the highest occupied molecular orbital. Since each of these three cluster sizes correspond to the completion of a first coordination shell, they can be considered as "isomeric motifs of the first coordination shell". Differences in the photoelectron anisotropy, the vertical ionization energies and the enthalpies of vaporization between Li(CH3OCH3) n and Na(CH3OCH3) n can be rationalized in terms of differences in their solvation shells, atomic ionization energies, polarizabilities, metal-oxygen bonds, ligand-ligand interactions and by cooperative effects.

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 26.5 eV for ionization from the three outermost valence orbitals. The measurements probe the evolution of the photoelectron anisotropy parameter ß as a function of cluster size. A remarkably steep decrease of ß with increasing cluster size is observed, which for the largest clusters reaches liquid bulk values. Detailed electron scattering calculations reveal that neither gas nor condensed phase scattering can explain the cluster data. Qualitative agreement between experiment and simulations is obtained with scattering calculations that treat cluster scattering as an intermediate case between gas and condensed phase scattering.

Low-energy photoelectron transmission through aerosol overlayers.

The transmission of low-energy (<1.8 eV) photoelectrons through the shell of core-shell aerosol particles is studied for liquid squalane, squalene, and di-ethyl-hexyl-sebacate shells. The photoelectrons are exclusively formed in the core of the particles by two-photon ionization. The total photoelectron yield recorded as a function of shell thicknesses (1-80 nm) shows a bi-exponential attenuation. For all substances, the damping parameter for shell thicknesses below 15 nm lies around 8 to 9 nm and is tentatively assigned to the electron attenuation length at electron kinetic energies of ≲1 eV. The significantly larger damping parameters for thick shells (>20 nm) are presumably a consequence of distorted core-shell structures. A first comparison of aerosol and traditional thin film overlayer methods is provided.

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. The cluster data and a detailed electron scattering model are used to predict the anisotropy of slow photoelectrons in liquid water. Reasonable agreement with experimental liquid jet data is found.

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±2.2 mole%. The smallest entity for the phase transition to be observed consists of approximately 100-200 solvent molecules. The quantification of this critical entity size is a stepping stone toward a deeper understanding of these quantum-classical solutions through direct modeling at the molecular level.

Solvated Electrons in Clusters: Magic Numbers for the Photoelectron Anisotropy.

This paper reports on a curiosity concerning magic numbers in neutral molecular clusters, namely on magic numbers related to the photoelectron anisotropy in angle-resolved photoelectron spectra. With a combination of density functional calculations and experiment, we search for magic numbers in Na(H2O)n, Na(NH3)n, Na(CH3OH)n, and Na(CH3OCH3)n clusters. In clusters of high symmetry, the highest occupied molecular orbital can be delocalized over an extended region, forming a symmetric charge distribution of high s character, which results in a pronounced anisotropy in the photoelectron angular distribution. We find magic numbers at n = 6 and 4 for sodium-doped dimethyl ether and ammonia clusters, respectively, but not for sodium-doped water and methanol clusters, which is likely a consequence of the degree of hydrogen bonding and the number of structural isomers.

Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters.

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem to be mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes but decrease slightly with increasing cluster size.

Electron mean free path from angle-dependent photoelectron spectroscopy of aerosol particles.

We propose angle-resolved photoelectron spectroscopy of aerosol particles as an alternative way to determine the electron mean free path of low energy electrons in solid and liquid materials. The mean free path is obtained from fits of simulated photoemission images to experimental ones over a broad range of different aerosol particle sizes. The principal advantage of the aerosol approach is twofold. First, aerosol photoemission studies can be performed for many different materials, including liquids. Second, the size-dependent anisotropy of the photoelectrons can be exploited in addition to size-dependent changes in their kinetic energy. These finite size effects depend in different ways on the mean free path and thus provide more information on the mean free path than corresponding liquid jet, thin film, or bulk data. The present contribution is a proof of principle employing a simple model for the photoemission of electrons and preliminary experimental data for potassium chloride aerosol particles.

Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer.

We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME - h6)n and (DME - d6)n n = 1 and 2, in the 9-14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C-H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH3OHCH3 (+) by the loss of CH2OCH3 with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME - h6)2 and deuterated (DME - d6)2, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME - d6 monomer.

Quantum state specific reactant preparation in a molecular beam by rapid adiabatic passage.

Highly efficient preparation of molecules in a specific rovibrationally excited state for gas/surface reactivity measurements is achieved in a molecular beam using tunable infrared (IR) radiation from a single mode continuous wave optical parametric oscillator (cw-OPO). We demonstrate that with appropriate focusing of the IR radiation, molecules in the molecular beam crossing the fixed frequency IR field experience a Doppler tuning that can be adjusted to achieve complete population inversion of a two-level system by rapid adiabatic passage (RAP). A room temperature pyroelectric detector is used to monitor the excited fraction in the molecular beam and the population inversion is detected and quantified using IR bleaching by a second IR-OPO. The second OPO is also used for complete population transfer to an overtone or combination vibration via double resonance excitation using two spatially separated RAP processes.