Ultrafast relaxation of photoexcited superfluid He nanodroplets.
ABSTRACT: 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.
Project description:Coherent diffractive imaging of individual free nanoparticles has opened routes for the in situ analysis of their transient structural, optical, and electronic properties. So far, single-shot single-particle diffraction was assumed to be feasible only at extreme ultraviolet and X-ray free-electron lasers, restricting this research field to large-scale facilities. Here we demonstrate single-shot imaging of isolated helium nanodroplets using extreme ultraviolet pulses from a femtosecond-laser-driven high harmonic source. We obtain bright wide-angle scattering patterns, that allow us to uniquely identify hitherto unresolved prolate shapes of superfluid helium droplets. Our results mark the advent of single-shot gas-phase nanoscopy with lab-based short-wavelength pulses and pave the way to ultrafast coherent diffractive imaging with phase-controlled multicolor fields and attosecond pulses.Diffraction imaging studies of free individual nanoparticles have so far been restricted to XUV and X-ray free - electron laser facilities. Here the authors demonstrate the possibility of using table-top XUV laser sources to image prolate shapes of superfluid helium droplets.
Project description:We investigate the photoinduced relaxation dynamics of Cr atoms embedded into superfluid helium nanodroplets. One- and two-color resonant two-photon ionization (1CR2PI and 2CR2PI, respectively) are applied to study the two strong ground state transitions z(7)P(2,3,4)° ← a(7)S3 and y(7)P(2,3,4)° ← a(7)S3. Upon photoexcitation, Cr* atoms are ejected from the droplet in various excited states, as well as paired with helium atoms as Cr*–He(n) exciplexes. For the y(7)P(2,3,4)° intermediate state, comparison of the two methods reveals that energetically lower states than previously identified are also populated. With 1CR2PI we find that the population of ejected z(5)P3° states is reduced for increasing droplet size, indicating that population is transferred preferentially to lower states during longer interaction with the droplet. In the 2CR2PI spectra we find evidence for generation of bare Cr atoms in their septet ground state (a(7)S3) and metastable quintet state (a(5)S2), which we attribute to a photoinduced fast excitation–relaxation cycle mediated by the droplet. A fraction of Cr atoms in these ground and metastable states is attached to helium atoms, as indicated by blue wings next to bare atom spectral lines. These relaxation channels provide new insight into the interaction of excited transition metal atoms with helium nanodroplets.
Project description:Molecules with their axes sharply confined in space, available through laser-induced alignment methods, are essential for many current experiments, including ultrafast molecular imaging. For these applications the aligning laser field should ideally be turned-off, to avoid undesired perturbations, and the strong alignment should last long enough that reactions and dynamics can be mapped out. Presently, this is only possible for small, linear molecules and for times less than 1?picosecond. Here, we demonstrate strong, field-free alignment of large molecules inside helium nanodroplets, lasting >10?picoseconds. One-dimensional or three-dimensional alignment is created by a slowly switched-on laser pulse, made field-free through rapid pulse truncation, and retained thanks to the impeding effect of the helium environment on molecular rotation. The opportunities field-free aligned molecules open are illustrated by measuring the alignment-dependent strong-field ionization yield of dibromothiophene oligomers. Our technique will enable molecular frame experiments, including ultrafast excited state dynamics, on a variety of large molecules and complexes.
Project description:The study of highly photo-excited matter at solid state density is an emerging field of research, which is benefitting the development of free-electron-laser (FEL) technology. We report an extreme ultraviolet (XUV) reflectivity experiment from a titanium (Ti) sample irradiated with ultrafast seeded FEL pulses at variable incident photon fluence and frequency. Using a Drude formalism we relate the observed increase in reflectivity as a function of the excitation fluence to an increase in the plasma frequency, which allows us to estimate the free electron density in the excited sample. The extreme simplicity of the experimental setup makes the present approach potentially a valuable complementary tool to determine the average ionization state of the excited sample, information of primary relevance for understanding the physics of matter under extreme conditions.
Project description:Dynamics following excitation with attosecond extreme ultraviolet (XUV) pulses arise from enormous numbers of accessible excited states, complicating the retrieval of state-specific time evolutions. We develop attosecond XUV multidimensional spectroscopy here to separate interfering pathways on a near-infrared (NIR) energy axis, retrieving single state dynamics in argon atoms in a two-dimensional (2D) XUV-NIR spectrum. In this experiment, we measure four-wave mixing signal arising from the interaction of XUV attosecond pulses centered around 15 eV with two few-cycle NIR pulses. The 2D spectrum is created by measuring the emitted XUV signal field spectrum while applying narrowband amplitude and phase modulations to one of the NIR pulses. Application of such a technique to systems of high dimensionality will provide for the observation of state-resolved pure electronic dynamics, in direct analogy to phenomena unraveled by multidimensional spectroscopies at optical frequencies.
Project description:Ultrafast extreme ultraviolet (XUV) sources with a controllable polarization state are powerful tools for investigating the structural and electronic as well as the magnetic properties of materials. However, such light sources are still limited to only a few free-electron laser facilities and, very recently, to high-order harmonic generation from noble gases. Here we propose and numerically demonstrate a laser-plasma scheme to generate bright XUV pulses with fully controlled polarization. In this scheme, an elliptically polarized laser pulse is obliquely incident on a plasma surface, and the reflected radiation contains pulse trains and isolated circularly or highly elliptically polarized attosecond XUV pulses. The harmonic polarization state is fully controlled by the laser-plasma parameters. The mechanism can be explained within the relativistically oscillating mirror model. This scheme opens a practical and promising route to generate bright attosecond XUV pulses with desirable ellipticities in a straightforward and efficient way for a number of applications.
Project description:Chromium (Cr) atoms embedded into helium nanodroplets (HeN) are ejected from the droplets upon photoexcitation. During ejection they undergo electronic relaxation resulting in bare Cr atoms in various excited states. In a study of the relaxation process we present absorption spectra observed via laser induced fluorescence and beam depletion as well as dispersed fluorescence spectra and time-resolved fluorescence measurements. Broad and shifted absorption structures were found for the strong z(7)P° ← a(7)S3 and y(7)P° ← a(7)S3 excitations from the ground state. Emission lines are, in contrast, very narrow, which indicates that fluorescence is obtained from bare excited Cr atoms after ejection. Upon excitation into the y(7)P2,3,4° states we observed fluorescence from y(7)P2°, z(5)P1,2,3°, and z(7)P2,3,4°, indicating that these states are populated by electronic relaxation during the ejection processes. Relative population ratios are obtained from the intensities of individual spectral lines. Excitation into the z(7)P2,3,4° states resulted in fluorescence only from z(7)P2°. Estimates of the time duration of the ejection process are obtained from time-resolved measurements.
Project description:Helium droplets provide the possibility to study phenomena at the very low temperatures at which quantum mechanical effects are more pronounced and fewer quantum states have significant occupation probabilities. Understanding the migration of either positive or negative charges in liquid helium is essential to comprehend charge-induced processes in molecular systems embedded in helium droplets. Here, we report the resonant formation of excited metastable atomic and molecular helium anions in superfluid helium droplets upon electron impact. Although the molecular anion is heliophobic and migrates toward the surface of the helium droplet, the excited metastable atomic helium anion is bound within the helium droplet and exhibits high mobility. The atomic anion is shown to be responsible for the formation of molecular dopant anions upon charge transfer and thus, we clarify the nature of the previously unidentified fast exotic negative charge carrier found in bulk liquid helium.
Project description:Ultrafast spectroscopy with attosecond resolution has enabled the real time observation of ultrafast electron dynamics in atoms, molecules and solids. These experiments employ attosecond pulses or pulse trains and explore dynamical processes in a pump-probe scheme that is selectively sensitive to electronic state of matter via photoelectron or XUV absorption spectroscopy or that includes changes of the ionic state detected via photo-ion mass spectrometry. Here, we demonstrate how the implementation of combined photo-ion and absorption spectroscopy with attosecond resolution enables tracking the complex multidimensional excitation and decay cascade of an Auger auto-ionization process of a few femtoseconds in highly excited krypton. In tandem with theory, our study reveals the role of intermediate electronic states in the formation of multiply charged ions. Amplitude tuning of a dressing laser field addresses different groups of decay channels and allows exerting temporal and quantitative control over the ionization dynamics in rare gas atoms.
Project description:The interaction of an electronically excited, single chromium (Cr) atom with superfluid helium nanodroplets of various size (10 to 2000 helium (He) atoms) is studied with helium density functional theory. Solvation energies and pseudo-diatomic potential energy surfaces are determined for Cr in its ground state as well as in the y(7)P, a(5)S, and y(5)P excited states. The necessary Cr-He pair potentials are calculated by standard methods of molecular orbital-based electronic structure theory. In its electronic ground state the Cr atom is found to be fully submerged in the droplet. A solvation shell structure is derived from fluctuations in the radial helium density. Electronic excitations of an embedded Cr atom are simulated by confronting the relaxed helium density (ρHe), obtained for Cr in the ground state, with interaction pair potentials of excited states. The resulting energy shifts for the transitions z(7)P ← a(7)S, y(7)P ← a(7)S, z(5)P ← a(5)S, and y(5)P ← a(5)S are compared to recent fluorescence and photoionization experiments.