Vacuum Ultraviolet Free Electron Laser Research Articles

Multi-functional gas cell in the vacuum ultraviolet free-electron laser beamline.

A long gas cell, filled with noble gas, is typically positioned between the undulator and the first mirror in the free-electron laser (FEL) beamline to attenuate the laser power as required by the end-stations. In addition to attenuation, the gas cell also serves important functions in various applications, such as spectrometer calibration, resolving power evaluation during beamline commissioning, and filtering of third harmonic in FEL operations. These functions of the gas cell have been successfully tested and implemented at the Dalian Coherent Light Source, a vacuum ultraviolet FEL facility located in Dalian, China. The resolving power of higher than 5000 has been obtained, and accurate calibration has been completed using the gas cell. During operation, the third harmonic of the FEL was attenuated by approximately one order of magnitude with almost the same power of the fundamental. This greatly improved the signal-to-noise ratio at the end-stations.

Size-Specific Infrared Spectroscopy of Neutral Hydrated Clusters Based on a Vacuum Ultraviolet Free Electron Laser.

Spectroscopic study of neutral hydrated clusters provides microscopic insights into the local structures and dynamics of complex systems but is very challenging because of the difficulty in size discrimination. Recently, we developed infrared (IR) spectroscopy based on threshold ionization using a tunable vacuum ultraviolet free electron laser (VUV-FEL). This experimental method allows for size-specific IR spectroscopic measurement of numerous neutral clusters without confinement, such as messenger tags, ultraviolet chromophores, and host matrix. This Perspective aims to highlight the latest advances in VUV-FEL-based IR spectroscopic studies on the confinement-free neutral amine-water, sulfur dioxide-water, and metal-water clusters. Fruitful collaborations with high-level quantum chemical calculations are reviewed. Future research directions with relevance to the atmosphere, biology, and catalysis are proposed.

Spectroscopic and Theoretical Identifications of Two Structural Motifs of (H2O)10 Cluster.

Precise characterization of archetypal systems of aqueous hydrogen-bonding networks is essential for developing accurate potential functions and universal models of water. The structures of water clusters (H2O)n (n = 2-9) have been verified recently through size-specific infrared spectroscopy with a vacuum ultraviolet free electron laser (VUV-FEL) and quantum chemical studies. For (H2O)10, the pentagonal prism and butterfly motifs were proposed to be important building blocks and were observed in previous experiments. Here we report the size-specific infrared spectra of (H2O)10 via a joint experimental and theoretical study. Well-resolved spectra provide a unique signature for the coexistence of pentagonal prism and butterfly motifs. These (H2O)10 motifs develop from the dominant structures of (H2O)n (n = 8, 9) clusters. This work provides an intriguing prelude to the diverse structure of liquid water and opens avenues for size-dependent measurement of larger systems to understand the stepwise formation mechanism of hydrogen-bonding networks.

Effects of isoprene on the ozonolysis of Δ3-carene and β-caryophyllene: Mechanisms of secondary organic aerosol formation and cross-dimerization

Elucidating the mutual effects between the different volatile organic compounds (VOCs) is crucial for comprehending the formation mechanism of atmospheric secondary organic aerosols (SOA). Here, the mixed VOCs experiments of isoprene and Δ3-carene/β-caryophyllene were carried out in the presence of O3 using an indoor smog chamber. The suppression effect of isoprene was recognized by the scanning mobility particle sizer spectrometer, online vacuum ultraviolet free electron laser (VUV-FEL) photoionization aerosol mass spectrometry, and quantum chemical calculations. The results indicate that the suppression effect of isoprene on the ozonolysis of Δ3-carene and β-caryophyllene shows fluctuating and monotonous trends, respectively. The carbon content of the precursor could be the main factor for regulating the strength of the suppression effect. Plausible structures and formation mechanisms of several new products generated from the single VOC precursor and VOC-cross-reaction are proposed, which enrich the category of VOC oxidation products. Meanwhile, a new dimerization mechanism of the RO2 + R'O2 reaction is suggested, which offers an intriguing perspective on the gas phase formation process of particle phase accretion products. The present findings provide valuable insights into clarifying the pivotal roles played by isoprene in the interplay between different VOCs and understanding of SOA formation mechanisms of VOC mixtures, especially nearby the emission origins.

Effects of NO and SO2 on the secondary organic aerosol formation from isoprene photooxidation

Investigation of the effects of anthropogenic pollutants on the mass concentrations, particle number concentrations, and chemical compositions of secondary organic aerosol (SOA) formation is essential in understanding the photooxidation mechanism of volatile organic compounds but has been proven to be a very challenging experimental target because of their complex processes. Here, the effects of NO and SO2 on SOA formation from isoprene photooxidation were studied by a number of laboratory studies. The results indicate the accumulated O3 upon the NO conversion triggers the main oxidation reaction, by which the oxidants (i.e., OH and SO4−) are derived. The SOA mass concentrations and particle number concentrations are enhanced by NO under low NO concentrations but suppressed by NO under high NO concentrations, which are consistent with previous studies (Kroll et al., 2005, 2006). This could be rationalized that the large amount of accumulated O3 inhibit the multi-step isoprene oxidation and a large number of less oxidized products (m/z < 130) absorb or condense on the surface of existing particles, which decelerate the SOA nucleation and growth. The presence of SO2 accelerates the conversion of NO and the accumulation of O3, which promotes the main oxidation reaction of isoprene. New compounds are observed at m/z = 134, 137, 150, 152, and 179 measured by threshold photoionization (positive ion mode) with a tunable vacuum ultraviolet free electron laser and are found to be mainly formed from the isoprene oxidization by O3 and OH. The present findings provide both macroscopic and microscopic information to advance understanding of atmospheric components affected by the anthropogenic-biogenic interactions in the neighborhood of emission origins.

Wakefields in superconducting rf cavities and the impact on vacuum ultraviolet free-electron laser oscillator performance

Wakefields in superconducting rf cavities and the impact on vacuum ultraviolet free-electron laser oscillator performance

Exploring the vacuum ultraviolet photochemistry of astrochemically important triatomic molecules.

The recently constructed vacuum ultraviolet (VUV) free electron laser (FEL) at the Dalian Coherent Light Source (DCLS) is yielding a wealth of new and exquisitely detailed information about the photofragmentation dynamics of many small gas-phase molecules. This Review focuses particular attention on five triatomic molecules-H2O, H2S, CO2, OCS and CS2. Each shows excitation wavelength-dependent dissociation dynamics, yielding photofragments that populate a range of electronic and (in the case of diatomic fragments) vibrational and rotational quantum states, which can be characterized by different translational spectroscopy methods. The photodissociation of an isolated molecule from a well-defined initial quantum state provides a lens through which one can investigate how and why chemical reactions occur, and provides numerous opportunities for fruitful, synergistic collaborations with high-level ab initio quantum chemists. The chosen molecules, their photofragments and the subsequent chemical reaction networks to which they can contribute are all crucial in planetary atmospheres and in interstellar and circumstellar environments. The aims of this Review are 3-fold: to highlight new photochemical insights enabled by the VUV-FEL at the DCLS, notably the recently recognized central atom elimination process that is shown to contribute in all of these triatomic molecules; to highlight some of the potential implications of this rich photochemistry to our understanding of interstellar chemistry and molecular evolution within the universe; and to highlight other and future research directions in areas related to chemical reaction dynamics and astrochemistry that will be enabled by increased access to VUV-FEL sources.

Spectroscopic snapshot for neutral water nonamer (H2O)9: Adding a H2O onto a hydrogen bond-unbroken edge of (H2O)8.

Structural characterization of neutral water clusters is crucial to understanding the structures and properties of water, but it has been proven to be a challenging experimental target due to the difficulty in size selection. Here, we report the size-specific infrared spectra of confinement-free neutral water nonamer (H2O)9 based on threshold photoionization, using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals in the 3200-3350cm-1 region are observed, providing unique spectral signatures for the formation of an unprecedented (H2O)9 structure evolved by adding a ninth water molecule onto a hydrogen bond-unbroken edge of the (H2O)8 octamer with D2d symmetry. This nonamer structure coexists with the five previously identified structures that can be viewed as derived by inserting a ninth water molecule into a hydrogen bond-broken edge of the D2d/S4 octamer. These findings provide key microscopic information for systematic understanding of the formation and growth mechanism of dynamical hydrogen-bonding networks that are responsible for the structure and properties of condensed-phase water.

Infrared Spectroscopy of Stepwise Hydration Motifs of Sulfur Dioxide.

Experimental characterization of microscopic events and behaviors of SO2-H2O interactions is crucial to understanding SO2 atmospheric chemistry but has been proven to be very challenging due to the difficulty in size selection. Here, size-dependent development of SO2 hydrate structure and cluster growth in the SO2(H2O)n (n = 1-16) complexes was probed by infrared spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser. Spectral changes with cluster size demonstrate that the sandwich structure initially formed at n = 1 develops into cycle structures with the sulfur and oxygen atoms in a two-dimensional plane (n = 2 and 3) and then into three-dimensional cage structures (n ≥ 4). SO2 is favorably bound to the surface of larger water clusters. These stepwise features of SO2 hydration on various sized water clusters contribute to understanding the reactive sites and electrophilicity of SO2 on cloud droplets, which may have important atmospheric implications for studying the SO2-containing aerosol systems.

Infrared spectroscopic signature of the structural diversity of the water heptamer

As a key species in understanding the hydrogen-bonding network transitions between liquid water and ice, the neutral water heptamer is a challenging experimental target, owing to the richness of low-lying isomers. Here, we report the size-specific infrared spectra of confinement-free, neutral water heptamer (H2O)7 based on threshold photoionization using a tunable vacuum ultraviolet free electron laser. The complexity of the observed spectra indicates that many nearly isoenergetic isomers are present at finite temperatures. Two classes of prism- and cage-like structures are identified in a high-pressure pulsed supersonic expansion of water heptamer, in which the former is favored energetically at low temperatures and serves as a major contributor to the experimental spectrum. These findings provide key information for filling the gap between well-studied water hexamer and octamer.

Aerosol mass spectrometry of neutral species based on a tunable vacuum ultraviolet free electron laser.

A vacuum ultraviolet free electron laser (VUV-FEL) photoionization aerosol mass spectrometer (AMS) has been developed for online measurement of neutral compounds in laboratory environments. The aerosol apparatus is mainly composed of a smog chamber and a reflectron time-of-flight mass spectrometer (TOF-MS). The indoor smog chamber had a 2 m3 fluorinated ethylene propylene film reactor placed in a temperature- and humidity-controlled room, which was used to generate the aerosols. The aerosols were sampled via an inlet system consisting of a 100 μm orifice nozzle and aerodynamic lenses. The application of this VUV-FEL AMS to the α-pinene ozonolysis under different concentrations reveals two new compounds, for which the formation mechanisms are proposed. The present findings contribute to the mechanistic understanding of the α-pinene ozonolysis in the neighborhood of emission origins of α-pinene. The VUV-FEL AMS method has the potential for chemical analysis of neutral aerosol species during the new particle formation processes.

Vacuum ultraviolet free-electron laser photoionization mass spectrometry of alpha-pinene ozonolysis

α-pinene is the most abundant monoterpene that represents an important family of volatile organic compounds. Molecular identification of key transient compounds during the α-pinene ozonolysis has been proven to be a challenging experimental target because of a large number of intermediates and products involved. Here we exploit the recently developed hybrid instruments that integrate aerosol mass spectrometry with a vacuum ultraviolet free-electron laser to study the α-pinene ozonolysis. The experiments of α-pinene ozonolysis are performed in an indoor smog chamber, with reactor having a volume of 2 m3 which is made of fluorinated ethylene propylene film. Distinct mass spectral peaks provide direct experimental signatures of previously unseen compounds produced from the reaction of α-pinene with O3. With the aid of quantum chemical calculations, plausible mechanisms for the formation of these new compounds are proposed. These findings provide crucial information on fundamental understanding of the initial steps of α-pinene oxidation and the subsequent processes of new particle formation.

Flexible ptychography platform to expand the potential of imaging at free electron lasers.

Ptychography, a scanning coherent diffraction imaging method, can produce a high-resolution reconstruction of a sample and, at the same time, of the illuminating beam. The emergence of vacuum ultraviolet and X-ray free electron lasers (FELs) has brought sources with unprecedented characteristics that enable X-ray ptychography with highly intense and ultra-fast short-wavelength pulses. However, the shot-to-shot pulse fluctuations typical for FEL pulses and particularly the partial spatial coherence of self-amplified spontaneous emission (SASE) FELs lead to numerical complexities in the ptychographic algorithms and ultimately restrict the application of ptychography at FELs. We present a general adaptive forward model for ptychography based on automatic differentiation, which is able to perform reconstructions even under these conditions. We applied this model to the first ptychography experiment at FLASH, the Free electron LASer in Hamburg, and obtained a high-resolution reconstruction of the sample as well as the complex wavefronts of individual FLASH pulses together with their coherence properties. This is not possible with more common ptychography algorithms.

Photodissociation Dynamics of H2O via the Ẽ' (1B2) Electronic State.

Photodissociation dynamics of H2O via the Ẽ'1B2 state were studied using the high-resolution H atom photofragment translational spectroscopy method, in combination with the tunable vacuum ultraviolet free electron laser (VUV FEL). The measured translational energy spectra allow us to determine the respective quantum state population distributions for the nascent OH(X2Π) and OH(A2Σ+) photofragments. Analyses of the quantum state population distributions show both the ground and electronically excited OH fragments to be formed with moderate vibrational excitation but with highly rotational excitation. Unlike the dissociation via the lower-lying electronic states, where OH(X) is the major fragment, the OH(A) products are predominant via the Ẽ' state. These products are mainly ascribed to a fast dissociation on the B̃1A1 state surface after nonadiabatic transitions from the initial excited Ẽ' state to the B̃ state. Meanwhile, another dissociation pathway from the Ẽ' state to the 1B2 3pb2 state, followed by coupling to the 1A2 3pb2 state, is also observed, which yields the OH(X) + H and O(3P) + 2H products.

Vibrational Signature of Dynamic Coupling of a Strong Hydrogen Bond.

Elucidating the dynamic couplings of hydrogen bonds remains an important and challenging goal for spectroscopic studies of bulk systems, because their vibrational signatures are masked by the collective effects of the fluctuation of many hydrogen bonds. Here we utilize size-selected infrared spectroscopy based on a tunable vacuum ultraviolet free electron laser to unmask the vibrational signatures for the dynamic couplings in neutral trimethylamine-water and trimethylamine-methanol complexes, as microscopic models with only one single hydrogen bond holding two molecules. Surprisingly broad progression of OH stretching peaks with distinct intensity modulation over ∼700 cm-1 is observed for trimethylamine-water, while the dramatic reduction of this progression in the trimethylamine-methanol spectrum offers direct experimental evidence for the dynamic couplings. State-of-the-art quantum mechanical calculations reveal that such dynamic couplings are originated from strong Fermi resonance between the stretches of hydrogen-bonded OH and several motions of the solvent water/methanol, such as translation, rocking, and bending, which are significant in various solvated complexes commonly found in atmospheric and biological systems.

Infrared spectroscopy of neutral clusters based on a vacuum ultraviolet free electron laser

Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level, but it has been proven to be a grand challenge for neutral clusters because the absence of a charge makes it difficult for the size selection and detection. Infrared (IR) spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser (VUV-FEL) has recently been developed in the lab. The IR-VUV depletion and IR+VUV enhancement spectroscopic techniques open new avenues for size-selected IR spectroscopies of a large variety of neutral clusters without confinement (i.e., an ultraviolet chromophore, a messenger tag, or a host matrix). The spectroscopic principles have been demonstrated by investigations of some neutral water clusters and some metal carbonyls. Here, the spectroscopic principles and their applications for neutral clusters are reviewed.

Infrared spectroscopic study of hydrogen bonding topologies in the smallest ice cube

The water octamer with its cubic structure consisting of six four-membered rings presents an excellent cluster system for unraveling the cooperative interactions driven by subtle changes in the hydrogen-bonding topology. Despite prediction of many distinct structures, it has not been possible to extract the structural information encoded in their vibrational spectra because this requires size-selectivity of the neutral clusters with sufficient resolution to identify the contributions of the different isomeric forms. Here we report the size-specific infrared spectra of the isolated cold, neutral water octamer using a scheme based on threshold photoionization using a tunable vacuum ultraviolet free electron laser. A plethora of sharp vibrational bands features are observed. Theoretical analysis of these patterns reveals the coexistence of five cubic isomers, including two with chirality. The relative energies of these structures are found to reflect topology-dependent, delocalized multi-center hydrogen-bonding interactions. These results demonstrate that even with a common structural motif, the degree of cooperativity among the hydrogen-bonding network creates a hierarchy of distinct species. The implications of these results on possible metastable forms of ice are speculated.

Electronically Excited OH Super-rotors from Water Photodissociation by Using Vacuum Ultraviolet Free-Electron Laser Pulses.

The fragmentation dynamics of water in a superexcited state play an important role in the ionosphere of the planets and in the photodissociation region (PDR) of the planetary nebula. In this Letter, we experimentally study the fragmentation dynamics of H2O with the energy above its ionization potential initiated by vacuum ultraviolet free-electron laser pulses. The experimental results indicate that the binary fragmentation channels H + OH and the triple channels O + 2H both present at 96.4 nm photolysis. Electronically excited OH super-rotors (v = 0, N ≥ 36, or v = 1, N ≥ 34), with the internal energy just above the OH (A) dissociation energy, are observed for the first time, which are only supported by the large centrifugal barriers. An absolute cross section of these super-rotors is estimated to be 0.7(±0.3) × 10-18 cm2. The tunnelling rates of these extremely rotationally excited states are also analyzed. This work shows a spectacular example of energy transfer from a photon to fragment rotation through photodissociation.

Infrared spectroscopy of neutral water clusters at finite temperature: Evidence for a noncyclic pentamer

Infrared spectroscopic study of neutral water clusters is crucial to understanding of the hydrogen-bonding networks in liquid water and ice. Here we report infrared spectra of size-selected neutral water clusters, (H2O) n (n = 3-6), in the OH stretching vibration region, based on threshold photoionization using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals observed in the 3,500-3,600-cm-1 region of (H2O)5 provide unique spectral signatures for the formation of a noncyclic pentamer, which coexists with the global-minimum cyclic structure previously identified in the gas phase. The main features of infrared spectra of the pentamer and hexamer, (H2O) n (n = 5 and 6), span the entire OH stretching band of liquid water, suggesting that they start to exhibit the richness and diversity of hydrogen-bonding networks in bulk water.

Vacuum-Ultraviolet Photon Detections.

Vacuum-ultraviolet (VUV) photon detection technology is an effective means for the exploration in the field of space science (monitoring the formation and evolution of solar storms), high-energy physics (dark matter detection), large-scale scientific facility (VUV free electron lasers) and electronic industry (high-resolution lithography). The advancement of this technology mainly depends on the performance optimization of VUV photodetectors. In this review, we introduced the research progress on the typical VUV photodetectors based on scintillator, photomultiplier tube, semiconductor, and gas, with their unique advantages and optimal performance indicators in different applications summarized. In particular, during recent years, thanks to the advances in ultra-wide bandgap semiconductors, economical VUV photodetectors with low power consumption and small size have been encouragingly developed. Finally, we pointed out the remaining challenges for each type of VUV detector, with the aim of maximizing the performance in a variety of applications in the future.