Flash melting amorphous ice.

Water can be vitrified if it is cooled at high rates, which makes it possible to outrun crystallization in so-called no man's land, a range of deeply supercooled temperatures where water crystallizes rapidly. Here, we study the reverse process in pure water samples by flash melting amorphous ice with microsecond laser pulses. Time-resolved electron diffraction reveals that the sample transiently crystallizes despite a heating rate of more than 5 × 106 K/s, even though under the same conditions, vitrification can be achieved with a similar cooling rate of 107 K/s. Moreover, we observe different crystallization kinetics for amorphous solid water and hyperquenched glassy water. These experiments open up new avenues for elucidating the crystallization mechanism of water and studying its dynamics in no man's land. They also add important insights into the laser melting and revitrification processes that are integral to the emerging field of microsecond time-resolved cryo-electron microscopy.

Atomic-Resolution Imaging of Fast Nanoscale Dynamics with Bright Microsecond Electron Pulses.

Atomic-resolution electron microscopy is a crucial tool to elucidate the structure of matter. Recently, fast electron cameras have added the time domain to high-resolution imaging, allowing static images to be acquired as movies from which sample drift can later be removed computationally and enabling real-time observations of atomic-scale dynamics on the millisecond time scale. Even higher time resolution can be achieved with short electron pulses, yet their potential for atomic-resolution imaging remains unexplored. Here, we generate high-brightness microsecond electron pulses from a Schottky emitter whose current we briefly drive to near its limit. We demonstrate that drift-corrected imaging with such pulses can achieve atomic resolution in the presence of much larger amounts of drift than with a continuous electron beam. Moreover, such pulses enable atomic-resolution observations on the microsecond time scale, which we employ to elucidate the crystallization pathways of individual metal nanoparticles as well as the high-temperature transformation of perovskite nanocrystals.

Visualizing Nanoscale Dynamics with Time-resolved Electron Microscopy.

The large number of interactions in nanoscale systems leads to the emergence of complex behavior. Understanding such complexity requires atomic-resolution observations with a time resolution that is high enough to match the characteristic timescale of the system. Our laboratory's method of choice is time-resolved electron microscopy. In particular, we are interested in the development of novel methods and instrumentation for high-speed observations with atomic resolution. Here, we present an overview of the activities in our laboratory.

Time-resolved formation of excited atomic and molecular states in XUV-induced nanoplasmas in ammonia clusters.

High intensity XUV radiation from a free-electron laser (FEL) was used to create a nanoplasma inside ammonia clusters with the intent of studying the resulting electron-ion interactions and their interplay with plasma evolution. In a plasma-like state, electrons with kinetic energy lower than the local collective Coulomb potential of the positive ionic core are trapped in the cluster and take part in secondary processes (e.g. electron-impact excitation/ionization and electron-ion recombination) which lead to subsequent excited and neutral molecular fragmentation. Using a time-delayed UV laser, the dynamics of the excited atomic and molecular states are probed from -0.1 ps to 18 ps. We identify three different phases of molecular fragmentation that are clearly distinguished by the effect of the probe laser on the ionic and electronic yield. We propose a simple model to rationalize our data and further identify two separate channels leading to the formation of excited hydrogen.

Three-Dimensional Shapes of Spinning Helium Nanodroplets.

A significant fraction of superfluid helium nanodroplets produced in a free-jet expansion has been observed to gain high angular momentum resulting in large centrifugal deformation. We measured single-shot diffraction patterns of individual rotating helium nanodroplets up to large scattering angles using intense extreme ultraviolet light pulses from the FERMI free-electron laser. Distinct asymmetric features in the wide-angle diffraction patterns enable the unique and systematic identification of the three-dimensional droplet shapes. The analysis of a large data set allows us to follow the evolution from axisymmetric oblate to triaxial prolate and two-lobed droplets. We find that the shapes of spinning superfluid helium droplets exhibit the same stages as classical rotating droplets while the previously reported metastable, oblate shapes of quantum droplets are not observed. Our three-dimensional analysis represents a valuable landmark for clarifying the interrelation between morphology and superfluidity on the nanometer scale.

Helium-induced electronic transitions in photo-excited Ba+-Hen exciplexes.

The possibility for helium-induced electronic transitions in a photo-excited atom is investigated using Ba+ excited to the 6p 2P state as a prototypical example. A diabatization scheme has been designed to obtain the necessary potential energy surfaces and couplings for complexes of Ba+ with an arbitrary number of helium atoms. It involves computing new He-Ba+ electronic wave functions and expanding them in determinants of the non-interacting complex. The 6p 2P ← 6s 2S photodissociation spectrum of He⋯Ba+ calculated with this model shows very weak coupling for a single He atom. However, several electronic relaxation mechanisms are identified, which could potentially explain the expulsion of barium ions from helium nanodroplets observed experimentally upon Ba+ photoexcitation. For instance, an avoided crossing in the ring-shaped He7Ba+ structure is shown to provide an efficient pathway for fine structure relaxation. Symmetry breaking by either helium density fluctuations or vibrations can also induce efficient relaxation in these systems, e.g., bending vibrations in the linear He2Ba+ excimer. The identified relaxation mechanisms can provide insight into helium-induced non-adiabatic transitions observed in other systems.

Harmonium: An Ultrafast Vacuum Ultraviolet Facility.

Harmonium is a vacuum ultraviolet (VUV) photon source built within the Lausanne Centre for Ultrafast Science (LACUS). Utilising high harmonic generation, photons from 20-110 eV are available to conduct steady-state or ultrafast photoelectron and photoion spectroscopies (PES and PIS). A pulse preserving monochromator provides either high energy resolution (70 meV) or high temporal resolution (40 fs). Three endstations have been commissioned for: a) PES of liquids; b) angular resolved PES (ARPES) of solids and; c) coincidence PES and PIS of gas phase molecules or clusters. The source has several key advantages: high repetition rate (up to 15 kHz) and high photon flux (1011 photons per second at 38 eV). The capabilities of the facility complement the Swiss ultrafast and X-ray community (SwissFEL, SLS, NCCR MUST, etc.) helping to maintain Switzerland's leading role in ultrafast science in the world.

Dynamics of photoexcited Ba(+) cations in (4)He nanodroplets.

We present a joint experimental and theoretical study on the desolvation of Ba(+) cations in (4)He nanodroplets excited via the 6p ← 6s transition. The experiments reveal an efficient desolvation process yielding mainly bare Ba(+) cations and Ba(+)Hen exciplexes with n = 1 and 2. The speed distributions of the ions are well described by Maxwell-Boltzmann distributions with temperatures ranging from 60 to 178 K depending on the excitation frequency and Ba(+) Hen exciplex size. These results have been analyzed by calculations based on a time-dependent density functional description for the helium droplet combined with classical dynamics for the Ba(+). In agreement with experiment, the calculations reveal the dynamical formation of exciplexes following excitation of the Ba(+) cation. In contrast to experimental observation, the calculations do not reveal desolvation of excited Ba(+) cations or exciplexes, even when relaxation pathways to lower lying states are included.

The Low Density Matter (LDM) beamline at FERMI: optical layout and first commissioning.

The Low Density Matter (LDM) beamline has been built as part of the FERMI free-electron laser (FEL) facility to serve the atomic, molecular and cluster physics community. After the commissioning phase, it received the first external users at the end of 2012. The design and characterization of the LDM photon transport system is described, detailing the optical components of the beamline.

Excitation of Sodium Atoms Attached to Helium Nanodroplets: The 3p ← 3s Transition Revisited.

The dynamics of Na atoms on the surface of helium nanodroplets following excitation via the 3p ← 3s transition has been investigated using state-specific ion-based detection of the products. Excitation of the system to the 3p (2)Π states is found to lead to the desorption of both bare Na and NaHe exciplexes. The associated speed distributions point to an impulsive desorption process for Na products and a thermally driven process for the NaHe exciplexes. In contrast, excitation of the 3p (2)Σ state leads exclusively to the impulsive desorption of Na atoms. In this case, the desorption is accompanied by a helium-induced relaxation process, as evidenced by the large fraction of detected Na (2)P1/2 atoms. The relaxation process is thought to be related to a crossing between the (2)Π1/2 and (2)Σ potential energy curves at large distance.

Dynamics of excited sodium atoms attached to helium nanodroplets.

The dynamics of laser-excited sodium atoms at the surface of helium nanodroplets has been investigated as a function of quantum state. For all cases, excitation of the system leads to desorption of the sodium atom from the droplet surface. The mean kinetic energy of the desorbed atoms scales linearly with excitation frequency, indicative of an impulsive desorption process. The energy partitioning between the helium and the desorbing sodium atom depends on the quantum state and appears to be related to the size and shape of the electron orbital. The speed distributions of desorbed NaHe exciplexes point toward a direct formation process of an exciplex with no internal energy. Photoelectron spectroscopy reveals an increasing importance of helium-induced relaxation with increasing quantum state, which is tentatively attributed to curve crossing between different NaHeN interaction potentials during the desorption process.

Communication: nucleation of quantized vortex rings in 4He nanodroplets.

Whereas most of the phenomena associated with superfluidity have been observed in finite-size helium systems, the nucleation of quantized vortices has proven elusive. Here we show using time-dependent density functional simulations that the solvation of a Ba(+) ion created by photoionization of neutral Ba at the surface of a (4)He nanodroplet leads to the nucleation of a quantized ring vortex. The vortex is nucleated on a 10 ps timescale at the equator of a solid-like solvation structure that forms around the Ba(+) ion. The process is expected to be quite general and very efficient under standard experimental conditions.

Shaped Laser Pulses for Microsecond Time-Resolved Cryo-EM: Outrunning Crystallization during Flash Melting.

Water vitrifies if cooled at rates above 3 × 105 K/s. In contrast, when the resulting amorphous ice is flash heated, crystallization occurs even at a more than 10 times higher heating rate, as we have recently shown. This may present an issue for microsecond time-resolved cryo-electron microscopy experiments, in which vitreous ice samples are briefly melted with a laser pulse because transient crystallization could potentially alter the dynamics of the embedded proteins. Here, we demonstrate how shaped microsecond laser pulses can be used to increase the heating rate and outrun crystallization. Time-resolved electron diffraction experiments reveal that the critical heating rate for amorphous solid water (ASW) is about 108 K/s. Our experiments add to the toolbox of the emerging field of microsecond time-resolved cryo-electron microscopy by demonstrating a straightforward approach for avoiding crystallization during laser melting and for achieving significantly higher heating rates, which paves the way for nanosecond time-resolved experiments.

Critical Landau velocity in helium nanodroplets.

The best-known property of superfluid helium is the vanishing viscosity that objects experience while moving through the liquid with speeds below the so-called critical Landau velocity. This critical velocity is generally considered a macroscopic property as it is related to the collective excitations of the helium atoms in the liquid. In the present work we determine to what extent this concept can still be applied to nanometer-scale, finite size helium systems. To this end, atoms and molecules embedded in helium nanodroplets of various sizes are accelerated out of the droplets by means of optical excitation, and the speed distributions of the ejected particles are determined. The measurements reveal the existence of a critical velocity in these systems, even for nanodroplets consisting of only a thousand helium atoms. Accompanying theoretical simulations based on a time-dependent density functional description of the helium confirm and further elucidate this experimental finding.

Translational dynamics of photoexcited atoms in 4He nanodroplets: the case of silver.

The dynamics following the photoexcitation of Ag atoms in (4)He nanodroplets via the 5p (2)P1/2 ← 5s (2)S1/2 and 5p (2)P3/2 ← 5s (2)S1/2 transitions has been investigated in a joint experimental and theoretical effort. It has been experimentally found that upon excitation to the (2)P1/2 state, the Ag atoms are ejected with a speed distribution peaking at about 55 m s(-1). When Ag is excited to the (2)P3/2 state, a rich phenomenology is found. While a fraction of the impurities remains solvated, the impurities that are ejected from the droplets either as Ag or AgHe have speed distributions similar, but not identical, to those found for excitation to the (2)P1/2 state. The experimental findings are qualitatively analyzed within a three-dimensional, time-dependent density functional approach for the helium droplet. The dynamics of the Ag-(4)He1000 system has been followed for several tens of picoseconds, long enough to observe AgHe exciplex formation and the departure of the photoexcited Ag atom from the helium droplet.

Charge transfer and penning ionization of dopants in or on helium nanodroplets exposed to EUV radiation.

Helium nanodroplets are widely used as a cold, weakly interacting matrix for spectroscopy of embedded species. In this work, we excite or ionize doped He droplets using synchrotron radiation and study the effect onto the dopant atoms depending on their location inside the droplets (rare gases) or outside at the droplet surface (alkali metals). Using photoelectron-photoion coincidence imaging spectroscopy at variable photon energies (20-25 eV), we compare the rates of charge-transfer to Penning ionization of the dopants in the two cases. The surprising finding is that alkali metals, in contrast to the rare gases, are efficiently Penning ionized upon excitation of the (n = 2)-bands of the host droplets. This indicates rapid migration of the excitation to the droplet surface, followed by relaxation, and eventually energy transfer to the alkali dopants.

Fast viral dynamics revealed by microsecond time-resolved cryo-EM.

Observing proteins as they perform their tasks has largely remained elusive, which has left our understanding of protein function fundamentally incomplete. To enable such observations, we have recently proposed a technique that improves the time resolution of cryo-electron microscopy (cryo-EM) to microseconds. Here, we demonstrate that microsecond time-resolved cryo-EM enables observations of fast protein dynamics. We use our approach to elucidate the mechanics of the capsid of cowpea chlorotic mottle virus (CCMV), whose large-amplitude motions play a crucial role in the viral life cycle. We observe that a pH jump causes the extended configuration of the capsid to contract on the microsecond timescale. While this is a concerted process, the motions of the capsid proteins involve different timescales, leading to a curved reaction path. It is difficult to conceive how such a detailed picture of the dynamics could have been obtained with any other method, which highlights the potential of our technique. Crucially, our experiments pave the way for microsecond time-resolved cryo-EM to be applied to a broad range of protein dynamics that previously could not have been observed. This promises to fundamentally advance our understanding of protein function.

Electron diffraction of deeply supercooled water in no man's land.

A generally accepted understanding of the anomalous properties of water will only emerge if it becomes possible to systematically characterize water in the deeply supercooled regime, from where the anomalies appear to emanate. This has largely remained elusive because water crystallizes rapidly between 160 K and 232 K. Here, we present an experimental approach to rapidly prepare deeply supercooled water at a well-defined temperature and probe it with electron diffraction before crystallization occurs. We show that as water is cooled from room temperature to cryogenic temperature, its structure evolves smoothly, approaching that of amorphous ice just below 200 K. Our experiments narrow down the range of possible explanations for the origin of the water anomalies and open up new avenues for studying supercooled water.

Near-atomic resolution reconstructions from in situ revitrified cryo samples.

A microsecond time-resolved version of cryo-electron microscopy (cryo-EM) has recently been introduced to enable observation of the fast conformational motions of proteins. The technique involves locally melting a cryo sample with a laser beam to allow the proteins to undergo dynamics in the liquid phase. When the laser is switched off, the sample cools within just a few microseconds and revitrifies, trapping particles in their transient configurations, in which they can subsequently be imaged. Two alternative implementations of the technique have previously been described, using either an optical microscope or performing revitrification experiments in situ. Here, it is shown that it is possible to obtain near-atomic resolution reconstructions from in situ revitrified cryo samples. Moreover, the resulting map is indistinguishable from that obtained from a conventional sample within the spatial resolution. Interestingly, it is observed that revitrification leads to a more homogeneous angular distribution of the particles, suggesting that revitrification may potentially be used to overcome issues of preferred particle orientation.