Coherent Vacuum Ultraviolet Radiation Research Articles

Giant enhancement of second harmonic generation via merging bound states in the continuum for vacuum ultraviolet radiation

Vacuum ultraviolet (VUV) light plays a crucial role in various scientific and technological fields, such as nanolithography and biomedical treatments. However, the inherent nonlinear optical coefficient of nonlinear optical crystals is typically very low, and increasing the action length is often necessary to improve the nonlinear conversion efficiency. This makes it challenging for these materials to achieve high-density optoelectronic integration at the micro-/nano-scale. In this study, we propose a design for generating coherent VUV radiation close to 175 nm using second harmonic generation (SHG) with an absolute efficiency exceeding 1.2‰ mW−1. This is achieved by merging multiple bound state in the continuum modes in a free-standing photonic crystal slab. Even with fabrication imperfections at a level lower than 10% disorder, the SHG efficiency of the samples remains robust, maintaining an efficiency of at least 2‰. This research provides a beneficial platform for generating efficient VUV light in the nanoscale.

Phase-coherence dynamics of frequency-comb emission via high-order harmonic generation in few-cycle pulse trains

Frequency-comb emission via high-order harmonic generation (HHG) provides an alternative method for the coherent vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) radiation at ultrahigh repetition rates. In particular, the temporal and spectral features of the HHG were shown to carry profound insight into frequency-comb emission dynamics. Here we present an ab initio investigation of the temporal and spectral coherence of the frequency comb emitted in HHG of He atom driven by few-cycle pulse trains. We find that the emission of frequency combs features a destructive and constructive coherences caused by the phase interference of HHG, leading to suppression and enhancement of frequency-comb emission. The results reveal intriguing and substantially different nonlinear optical response behaviors for frequency-comb emission via HHG. The dynamical origin of frequency-comb emission is clarified by analyzing the phase coherence in HHG processes in detail. Our results provide fresh insight into the experimental realization of selective enhancement of frequency comb in the VUV–XUV regimes.

PFI-ZEKE-photoelectron spectroscopy of N2O using narrow-band VUV laser radiation generated by four-wave mixing in Ar using a KBBF crystal.

A new nonlinear optical scheme relying on sum-frequency mixing in a KBe2BO3F2 crystal has been used to generate intense, broadly tunable, narrow-bandwidth, coherent vacuum-ultraviolet (VUV) radiation beyond 16 eV by resonance-enhanced four-wave mixing in Ar. The VUV radiation was used to record high-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the N2O+ A+ ← N2O X photoionizing transition in the wave-number range from 132 000 cm-1 to 135 000 cm-1. The rotational structure of almost all vibrational levels of the A+ state with vibrational term values up to 2700 cm-1 could be resolved, and improved values of the first two adiabatic ionization energies of N2O, corresponding to the formation of the X+ 2Π3/2(000) J+ = 3/2 and A+ 2Σ+(000) N+ = 0 levels of N2O+ from the X 1Σ+(000) J″ = 0 ground state [103 969.30(12) cm-1 and 132 197.70(12) cm-1, respectively], were derived. The rotational intensity distributions of the bands were found to depend strongly on the value of the vibrational angular momentum of the ionic levels. The vibrational structure is discussed in terms of previously reported effective-Hamiltonian analyses.

Quantum state-to-state vacuum ultraviolet photodissociation dynamics of small molecules

The present review focused on selected, recent experimental progress of photodissociation dynamics of small molecules covering the vacuum ultraviolet (VUV) range from 6 eV to 20 eV. These advancements come about due to the available laser based VUV light sources, along with the developments of advanced experimental techniques, including the velocity-map imaging (VMI), H-atom Rydberg tagging time-of-flight (HRTOF) techniques, as well as the two-color tunable VUV-VUV laser pump-probe detection method. The applications of these experimental techniques have allowed VUV photodissociation studies of many diatomic and triatomic molecules to quantum state-to-state in detail. To highlight the recent accomplishments, we have summarized the results on several important molecular species, including H2 (D2, HD), CO, N2, NO, O2, H2O (D2O, HOD), CO2, and N2O. The detailed VUV photodissociation studies of these molecules are of astrochemical and atmospheric relevance. Since molecular photodissociation initiated by VUV excitation is complex and is often governed by multiple electronic potential energy surfaces, the unraveling of the complex dissociation dynamics requires state-to-state cross section measurements. The newly constructed Dalian Coherent Light Source (DCLS), which is capable of generating coherent VUV radiation with unprecedented brightness in the range of 50–150 nm, promises to propel the photodissociation experiment to the next level.

Unravelling the dynamical origin of below- and near-threshold harmonic generation of H2+ in an intense NIR laser field.

Recently, the study of near- and below- threshold regime harmonics as a potential source of intense coherent vacuum-ultraviolet radiation has received considerable attention. However, the dynamical origin of these lower harmonics, particularly for the molecular systems, is less understood and largely unexplored. Here we perform the first fully ab initio and high precision 3D quantum study of the below- and near-threshold harmonic generation of molecules in an intense 800-nm near-infrared (NIR) laser field. Combining with a synchrosqueezing transform of the quantum time-frequency spectrum and an extended semiclassical analysis, we explore in-depth the roles of various quantum trajectories, including short- and long trajectories, multiphoton trajectories, resonance-enhanced trajectories, and multiple rescattering trajectories of the below- and near- threshold harmonic generation processes. Our results shed new light on the dynamical origin of the below- and near-threshold harmonic generation and various quantum trajectories for diatomic molecules for the first time.

Optimal crossed overlap of coherent vacuum ultraviolet radiation and thermal muonium emission for μSR with the Ultra Slow Muon

For μSR with ultra slow muon, we are constructing U line in materials and life science facility (MLF), J-PARC at present. Generation of ultra slow muon requires thermal muonium generation and laser resonant ionization process with vacuum ultraviolet radiation (1S→2P) and 355-nm radiation (2P→unbound). For laser resonant ionization, the coherent radiations and the thermal muonium emission must be coincident in time and space. The radiations can be steered in a chamber for reasonable overlap in space, and they can be easily overlapped in time because they are generated from one laser source. The trigger signal of the accelerator is useful for stable overlap in time.

Highly coherent vacuum ultraviolet radiation at the 15th harmonic with echo-enabled harmonic generation technique

Measurements of highly coherent vacuum ultraviolet radiation are produced with the echo-enabled harmonic generation technique.

Ultra Slow Muon Microscope at MUSE / J-PARC

We report current constructing states of the Ultra Slow Muon Beam at U-line / MUSE / J-PARC, which are supported by thermal muonium (Mu, μ+e−) production with the most intense pulsed slow muon beam, laser resonant ionization, and transportation of Ultra Slow Muon Beam. A thermal Mu is produced by a hot tungsten foil in a Mu-production chamber. At the laser resonant ionization process, a thermal Mu is ionized by coherent vacuum ultraviolet radiation and coherent 355-nm radiation. The coherent radiation sources are developed at RIKEN, installed in a laser cabin, and connected via a VUV steering chamber with the Mu-production chamber.

Resonance ionisation mass spectrometry of krypton and its applications in planetary science

A new resonance ionisation time-of-flight mass spectrometer for determining krypton isotope ratios in extraterrestrial samples is presented. Laser heating is used to extract gas from mg-size samples. A cryogenic sample concentrator is employed. Atoms continuously condense on a 75 K stainless steel substrate at the back plate of a Wiley-McLaren laser ion source from where they are desorbed by a pulsed 1064 nm laser and resonantly ionized in the plume. A three-colour (116.5 nm, 558.1 nm and 1064 nm) excitation scheme is used. Tuneable coherent Vacuum Ultraviolet (vuv) radiation near 116.5 nm is generated by four-wave sum frequency mixing of 252.5 nm and 1507 nm pulsed dye laser beams in a binary mixture of negatively and positively dispersive gases (Xe and Ar). Isotope effects have been observed that reduce the reproducibility of isotope ratio measurements between odd-mass, non-zero nuclear spin isotopes and even-mass, zero nuclear spin isotopes. This can be minimised and stabilised by controlling the laser fluences, experimental geometry, and the population of the magnetic sub-levels of the excited atomic states used in the ionisation process. Once stability is achieved, sample-standard bracketing (during which the known isotope ratios of a standard are determined before and after the measurements of the sample under the same conditions) allows precision and reproducibility of \(\sim \)1 % for the major isotope ratios to be achieved in samples \(\sim 10^{6}\) krypton atoms. Detection limits of \(<1000\) atoms/isotope have been demonstrated, ratios of \(^{81}\)Kr in meteorites have been made with \(\sim \)5–10 % precision. Applications of the instrument in various areas of planetary science are also discussed.

Photoelectron spectroscopy of anions at 118.2nm: Observation of high electron binding energies in superhalogens MCl4− (M=Sc, Y, La)

High energy photon is needed for photoelectron spectroscopy (PES) of anions with high electron binding energies, such as superhalogens and O-rich metal oxide clusters. The highest energy photon used for anion PES in the laboratory has been 157 nm (7.866 eV) from F2 eximer lasers. Here, we report an anion PES experiment using coherent vacuum ultraviolet radiation at 118.2 nm (10.488 eV) by tripling the third harmonic output (355 nm) of a Nd:YAG laser in a XeAr cell. Our study focuses on a set of superhalogen species, MCl(4) (-) (M=Sc, Y, La), which were expected to possess very high electron binding energies. While the 157 nm photon can only access the ground state detachment features for these species, more transitions to the excited states at binding energies higher than 8 eV are observed at 118.2 nm. The adiabatic detachment energies are shown to be, 6.84, 7.02, and 7.03 eV for ScCl(4) (-), YCl(4) (-), and LaCl(4) (-) eV, respectively, whereas their corresponding vertical detachment energies are measured to be 7.14, 7.31, and 7.38 eV.

One-photon mass-analyzed threshold ionization spectroscopy of CH2BrI: Extensive bending progression, reduced steric effect, and spin-orbit effect in the cation

One-photon mass-analyzed threshold ionization (MATI) spectrum of CH2BrI was obtained using coherent vacuum-ultraviolet radiation generated by four-wave difference-frequency mixing in Kr. Unlike CH2ClI investigated previously, a very extensive bending (Br-C-I) progression was observed. Vibrational frequencies of CH2BrI+ were measured from the spectra and the vibrational assignments were made by utilizing frequencies calculated by the density-functional-theory (DFT) method using relativistic effective core potentials with and without the spin-orbit terms. A noticeable spin-orbit effect on the vibrational frequencies was observed from the DFT calculations, even though its influence was not so dramatic as in CH2ClI+. A simple explanation based on the bonding characteristics of the molecular orbitals involved in the ionization is presented to account for the above differences between the MATI spectra of CH2BrI and CH2ClI. The 0-0 band of the CH2BrI spectrum could be identified through the use of combined data from calculations and experiments. The adiabatic ionization energy determined from the position of this band was 9.5944+/-0.0006 eV, which was significantly smaller than the vertical ionization energy reported previously.

Measurement of the autoionization lifetime of the superexcited atomic sulfur S(3s23p3(2Do)4d) state using tunable vacuum ultraviolet (VUV) radiation

A new method is described that combines a tunable coherent vacuum ultraviolet (VUV) radiation source and an ion velocity imaging apparatus to study the autoionization of superexcited sulfur atoms. The photolysis of CS2 at 193 nm is used to produce metastable sulfur atoms in the 1D2 state. The S(1D2) atom is then directly excited to the neutral superexcited state 3s23p3(2Do)4d (1Do2) at 11.317 eV with a tunable VUV photon at ~121.896 nm. This excited state then undergoes autoionization into the first ionization continuum state of S+(4So3/2) + e–, which is not directly accessible from the S(1D2) state through optical transition. By monitoring the S+ signal in the time-of-flight mass spectrometer while scanning the excitation wavelength, the line profile of the 3s23p34d 1Do2 ← 3s23p4 1D2 transition is recorded and found to have a full width at half maximum (FWHM) of 0.9 cm–1. This has been used to determine an autoionization lifetime of the neutral superexcited 3s23p34d 1Do2 state of 5.9 ps. The accurate measurement of the autoionization lifetime provides a benchmark for testing fundamental theoretical models of processes occurring in excited states of atoms. Key words: autoionization, atomic sulfur, vacuum ultraviolet (VUV), full width at half maximum (FWHM).

On-line analysis of organic components in fine and ultrafine particles by photoionization aerosol mass spectrometry.

A new method, photoionization aerosol mass spectrometry (PIAMS), is described for real-time analysis of organic components in airborne particles below approximately 300 nm in diameter. Particles are focused through an aerodynamic lens assembly into the mass spectrometer where they are collected on a probe in the source region. After a sufficient amount of sample has been collected, the probe is irradiated with a pulsed infrared laser beam to vaporize organic components, which are then softly ionized with coherent vacuum ultraviolet radiation at 118 nm (10.5 eV). Since the photon energy is close to the ionization energies of most organic compounds, fragmentation is minimized. Both aliphatic and aromatic compounds of atmospheric relevance are detected and quantified in the low- to midpicogram range. The photoionization signal intensity increases linearly with the amount of material sampled and is independent of particle size. The fragmentation induced by laser desorption is greater than that observed with thermal vaporization, suggesting that the internal energy imparted by the former is greater. Although some molecular fragmentation is observed, mass spectra from common sources of ambient organic aerosol are distinguishable and consistent with previous off-line measurements by gas chromatography/mass spectrometry. These results illustrate the potential of PIAMS for molecular characterization of organic aerosols in ambient and smog chamber measurements.

One-photon mass-analyzed threshold ionization spectroscopy of 2-bromopropene (2-C3H5Br): Analysis of vibration and internal rotation in the cation

Vibrational spectrum of 2-C3H5Br cation in the ground electronic state was obtained by one-photon mass-analyzed threshold ionization (MATI) spectroscopy using coherent vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. From the MATI spectra, ionization energy of 2-C3H5Br to the ionic ground state has been determined to be 9.4377±0.0006 eV. Vibrational assignments have been made by comparing with the vibrational frequencies and Franck-Condon factors calculated at the B3LYP and BP86 levels with the 6-311++G(3df,3pd) basis set. Several low-frequency bands have been assigned to the torsional motion of the methyl group in the cation. Energies of the torsional states and relative transition intensities to these states have been reproduced well by a one-dimensional rotor model. The torsional barrier and internal rotational constant have been determined to be 80.0 and 5.13 cm−1, respectively.

One-Photon Mass-Analyzed Threshold Ionization Spectroscopy of trans- and cis-1-C3H5Br: Ionization Energies and Vibrational Assignments for the Cations

Vibrational spectra of trans- and cis-1-C3H5Br cations in the ground electronic states were obtained by the one-photon mass-analyzed threshold ionization (MATI) spectroscopy using the coherent vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. From the MATI spectra, ionization energies of trans- and cis-1-C3H5Br to the ionic ground states have been determined to be 9.2693 ± 0.0006 and 9.3140 ± 0.0006 eV, respectively. Almost complete vibrational assignments for the peaks in the MATI spectra were possible by utilizing vibrational frequencies and Franck−Condon factors calculated at the B3LYP and BP86 levels with the 6-311++G(3df,3pd) basis set.

Vacuum ultraviolet mass-analyzed threshold ionization spectroscopy of vinyl bromide: Franck–Condon analysis and vibrational assignment

Vibrational spectrum of vinyl bromide cation in the ground electronic state was obtained by one-photon mass-analyzed threshold ionization (MATI) spectroscopy using coherent vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. From MATI spectrum, ionization energy to the ground state of the cation was determined to be 9.8171±0.0006 eV (79 180±5 cm−1). Almost complete vibrational assignments for the peaks in the MATI spectrum were possible by utilizing vibrational frequencies and Franck–Condon factors calculated at the Becke three parameter Lee–Yang–Parr (B3LYP)/6-311++G(df,pd) level. Franck–Condon analysis for one-photon MATI spectra is especially useful because calculations of only the ground electronic states are involved while that for two-photon MATI spectra requires excited state calculations.

Vacuum ultraviolet mass-analyzed threshold ionization spectroscopy of benzene: Vibrational analysis of C6H6+ and C6D6+ in the B̃ 2E2g state

Vibrational spectra of C6H6+ and C6D6+ in the first excited electronic state, B̃ 2E2g, have been measured by one-photon mass-analyzed threshold ionization spectroscopy using coherent vacuum ultraviolet radiation generated by four-wave sum frequency mixing in Hg. Ionization energies to C6H6+ and C6D6+ in the B̃ 2E2g state have been determined to be 11.4897±0.0006 and 11.5235±0.0006 eV, respectively. Vibrational spectra were much simpler than and different from those of the same state recorded by the gerade photo-induced Rydberg ionization technique reported previously. For some vibrations not much affected by the Jahn–Teller effect, assignments were possible by comparing with the calculated results. Assignments for the Jahn–Teller components were not definite, or rather arbitrary, even though decent fits were possible through multimode Jahn–Teller calculations.

Vacuum ultraviolet mass-analyzed threshold ionization spectroscopy of benzene: Vibrational analysis of C6H6+ and C6D6+ in the X̃ 2E1g state

Vibrational spectra of C6H6+ and C6D6+ in the ground electronic state have been measured by one-photon mass-analyzed threshold ionization (MATI) spectroscopy using coherent vacuum ultraviolet radiation generated by four wave mixing in Kr gas. The ionization energies of C6H6 and C6D6 determined by one-photon MATI, 74551±5 and 74579±5 cm−1, respectively, are similar to those reported previously. Vibrational spectra are much simpler than the previous zero kinetic energy photoelectron and MATI spectra obtained by two-photon excitation. Almost complete vibrational assignments for the cations have been possible, which will be useful for future theoretical studies of the Jahn-Teller effect in these cations. Implication from the present one-photon spectra agrees with the previous suggestion that the geometry of benzene cation in the ground electronic state belongs to the D6h symmetry.

Attosecond burst and high-harmonic generation in molecular ionization by ultrashort laser pulses

It is shown that the efficiency of attosecond pulse and high-harmonic generation in the ionization of excited molecular structures by a powerful femtosecond optical pulse can appreciably exceed the efficiency of analogous processes in atomic systems. This is due to the presence of a delocalized electron wave-packet component in the nonequilibrium molecular states, resulting in an increase of the number of particles that are effectively involved in the bremsstrahlung generation in the course of recollisions of laser-accelerated electrons with molecular core. Calculations suggest that, by optimizing the nonlinear response of molecular systems in the ionization process, one can develop compact sources of coherent vacuum ultraviolet and X-ray radiation with luminance at a level that is presently achieved only at large-scale accelerator facilities with free-electron lasers.

A new powerful source for coherent VUV radiation: Demonstration of exponential growth and saturation at the TTF free-electron laser

: We present experimental evidence that the free-electron laser at the TESLA Test Facility has reached the maximum power gain of 107 in the vacuum ultraviolet (VUV) region at wavelengths between 80 and 120 nm. At saturation the FEL emits short pulses with GW peak power and a high degree of transverse coherence. The radiation pulse length can be adjusted between 30 fs and 100 fs. Radiation spectra and fluctuation properties agree with the theory of high gain, single-pass free-electron lasers starting from shot noise.