Ion Yield Research Articles

Advances in response time of strong-field ionization of atoms

The response time of the electron to light in photoemission is difficult to define and measure. The tunneling ionization of atoms and molecules in a strong laser field is a type of strong field-induced photoelectric effect. In this process, the electron response time will change the time of high-order harmonic generation (HHG), which will have a fundamental influence on the reconstruction of electron attosecond dynamics through HHG. We propose a simple theory to resolve the response time problem in strong field atomic tunneling ionization. The response time corresponds to the strong interaction time of three bodies i.e. Coulomb, electron and laser field, which can be determined at the quantum-classical boundary. The observable directly obtained through response time can quantitatively reproduce a series of attoclock experimental curves and provide consistent explanations for these experimental phenomena. This work introduces the main conclusions of response time theory and summarizes in detail the research progress of this theory. Firstly, this theory can be applied to the orthogonal two-color laser field to quantitatively explain the main characteristic structures of photoelectron momentum distribution (PMD). Besides, with this response time theory, the scaling law of the observable in attoclock experiment can be obtained. The proposal of scaling law is expected to provide a systematical theoretical guide for better understanding the applicability or feasibility of the attoclock under different conditions. In addition, based on the atomic response time theory, we further consider the property of multi-center Coulomb potential of molecular and develop a response time theory suitable for molecular system. Subsequently, we further apply the response time theory to polar molecules, by utilizing the asymmetry of PMD closely related to response time to recognize the permanent dipole (PD) effect within the laser sub-cycle. In the end, we discuss the prospects for research on response time. Firstly, it is envisioned to further apply response time theory to weak light and single photon transition to detect the response time of related processes. Besides, considering the significant influence of response time on the property of time-domain of HHG electron trajectories, the recombination (re-scattering) effect based on the current strong field tunneling ionization response time theory can be further investigated, thus extending this theory to describing HHG and above threshold ionization (ATI) processes. Furthermore, designing the “re-scattering electron trajectories” reconstruction scheme based on the electron trajectories with response time correction will provide important suggestions for HHG spectroscopic experiments. Finally, considering the asymmetric ionization caused by the PD effect of polar molecules, if the net ionization yield of adjacent sub-cycles is used as the current indicator, polar molecules can be used as a “micro diode” to study a type of attosecond response switching device. Polar molecular diodes emit electrons through tunneling ionization in laser field. According to the response time theory, tunneling occurs almost instantaneously, and response time needs considering only at the tunneling exit. Based on this, by searching for suitable materials (such as two-dimensional materials), it is possible to design a type of semi-classical diode (which can utilize tunneling) with femtosecond or even sub-femtosecond response time. The response time theory can provide a convenient theoretical tool for designing of such tunneling diodes.

Single-photon ionization of SiC in the gas phase: experimental and ab initio characterization of SiC.

We report the first experimental observation of single-photon ionization transitions of the SiC radical between 8.0 and 11.0 eV performed on the DESIRS beamline at the SOLEIL synchrotron facility. The SiC radical, very difficult to synthesize in the gas phase, was produced through chemical reactions between CHx (x = 0-3) and SiHy (y = 0-3) in a continuous microwave discharge flow tube, the CHx and SiHy species being formed by successive hydrogen-atom abstractions induced by fluorine atoms on methane and silane, respectively. Mass-selected ion yield and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The photoelectron spectrum enables the first direct experimental determinations of the X+ 4Σ- ← X 3Π and 1+ 2Π ← X 3Π adiabatic ionization energies of SiC (8.978(10) eV and 10.216(24) eV, respectively). Calculated spectra based on Franck-Condon factors are compared with the experimental spectra. These spectra were obtained by solving the rovibrational Hamiltonian, using the potential energy curves calculated at the multireference single and double configuration interaction level with Davidson correction (MRCI + Q) and the aug-cc-pV5Z basis set. MRCI + Q calculations including the core and core-valence electron correlation were performed using the aug-cc-pCV6Z basis set to predict the spectroscopic properties of the six lowest electronic states of SiC+. Complete basis set extrapolations and relativistic energy corrections were also included in the determination of the energy differences characterizing the photoionization process. Using our experimental and theoretical results, we derived semi-experimental values for the five lowest ionization energies of SiC.

A hydrogen atom in strong elliptically polarized laser fields within discrete variable representation

The nondirect product discrete variable representation (npDVR) is developed for the time-dependent Schrödinger equation with nonseparable angular variables and is applied to a hydrogen atom in elliptically polarized strong laser fields. The 2D npDVR is constructed on spherical harmonics orthogonalized on the 2D angular grids of the Popov and Lebedev 2D cubatures for the unit sphere. With this approach we have investigated the dynamics of a hydrogen atom initially in its ground state in elliptically polarized laser fields with the intensity up to W cm−2 and a wavelength of λ = 800 nm. For these parameters of the laser field and the entire range of ellipticity variation, we have calculated the total excitation and ionization yields of the atom. The performed analysis of the method convergence shows that the achieved accuracy of our calculations significantly exceeds the accuracy of recent works of other authors relevant to the problem, due to the high efficiency of the 2D npDVR in approximating the angular part of the 3D time-dependent Schrödinger equation. We also propose a new simple procedure for infinite summation of the transition probabilities to the bound states of the hydrogen atom when calculating the total excitation yield and prove its accuracy by comparison with conventional methods. The obtained results show the potential prospects of the 2D npDVR for investigating atomic dynamics in stronger laser fields.

Generation of a controllable TNSA deuteron beam using deuterated metal targets

This study investigated the feasibility of using deuterated titanium targets for the generation of a target normal sheath acceleration (TNSA) deuteron beam. Commercial 25-μm-thick titanium foil was cut into 500 × 500-μm2 squares and subsequently deuterated using different approaches. The spectra and total yields of all emitted ions were measured using a Thomson parabola ion spectrometer. It was found that a 24-h exposure to 1 atm of D2 gas at 400 °C is the most-efficient deuteration method, producing yields in the mid-1011 deuterons per shot. The deuteron energy spectra changed from an exponential shape at low ion yields to exponentially modified Gaussians at higher yields. Simulations suggest that this effect is due to increased Coulomb interactions between the ions, which suppress the low energies. Separate campaigns will utilize the presented approach to produce a TNSA triton beam. Two such targets will be used in a pitcher/catcher configuration to study the tritium–tritium reaction T(t, 2n)α.

Controlling Fragmentation of the Acetylene Cation in the Vacuum Ultraviolet via Transient Molecular Alignment.

An open-loop control scheme of molecular fragmentation based on transient molecular alignment combined with single-photon ionization induced by a short-wavelength free electron laser (FEL) is demonstrated for the acetylene cation. Photoelectron spectra are recorded, complementing the ion yield measurements, to demonstrate that such control is the consequence of changes in the electronic response with molecular orientation relative to the ionizing field. We show that stable C2H2+ cations are mainly produced when the molecules are parallel or nearly parallel to the FEL polarization, while the hydrogen fragmentation channel (C2H2+ → C2H+ + H) predominates when the molecule is perpendicular to that direction, thus allowing one to distinguish between the two photochemical processes. The experimental findings are supported by state-of-the art theoretical calculations.

Disentangling Multiphoton Ionization and Dissociation Channels in Molecular Oxygen Using Photoelectron-Photoion Coincidence Imaging.

Multiphoton excitation of molecular oxygen in the 392-408 nm region is studied using a tunable femtosecond laser coupled with a double velocity map imaging photoelectron-photoion coincidence spectrometer. The laser intensity is held at ≤∼1 TW/cm2 to ensure excitation in the perturbative regime, where the possibility of resonance enhanced multiphoton ionization (REMPI) can be investigated. O2+ production is found to be resonance enhanced around 400 nm via three-photon excitation to the e'3Δu(v = 0) state, similar to results from REMPI studies using nanosecond dye lasers. O+ production reaches 7% of the total ion yield around 405 nm due to two processes: autoionization following five-photon excitation of O2, producing O2+(X(v)) in a wide range of vibrational states followed by two- or three-photon dissociation, or six-photon excitation to a superexcited O2** state followed by neutral dissociation and subsequent ionization of the electronically excited O atom. Coincidence detection is shown to be crucial in identifying these competing pathways.

Two-step photoionization of barium atoms through excited levels in optical dense approximation

The kinetics of two-step photoionization of barium atoms through excited levels was studied by numerical simulation method in the optically dense approximation. The first laser at wavelength nm ( nm) pumps transition (). The second laser with nm ( nm) ionizes atoms from the level (). The third probe laser with wavelength nm causes resonant fluorescence of barium ions. It is shown that the metastable from the triplet in barium is strongly populated through levels. Therefore, the applying of the ionizing laser tuned to a continuum from this metastable can yield a significant increase in the ionization efficiency. The laser-induced fluorescence method makes it possible to estimate the photoionization yield of barium ions with an error of up to 8%. The loading rate of the barium ion beam into the ion trap, obtained numerically, is consistent with the experimental data [Opt. Exp. 19(17), 16438 (2011)]. The deceleration of ultracold plasma recombination due to the heating of electrons in superelastic collisions for the characteristic times of a two-stage process is predicted.

High-resolution photoelectron spectroscopy of the ground and first excited electronic states of MgKr+

We report on the characterisation of the lowest three electronic states of MgKr, the X ground state associated with the Mg(3s) + Kr(4p) dissociation limit and the A and B excited states associated with the Mg(3p) + Kr(4p) dissociation limits. The vibrational structure of the X ground state was measured by pulsed-field-ionisation zero-kinetic-energy photoelectron spectroscopy starting from the a metastable state of MgKr generated by laser ablation of a Mg rod in a Kr supersonic beam. The vibrational assignment was derived from the isotopic structure of the spectra and the adiabatic ionisation energy of the ionising transition was determined to be 38182.4(2.0) cm. Partially rotationally resolved spectra of the A X and B X transitions were recorded by monitoring the yield of Mg ions produced by dissociation of MgKr using the technique of isolated-core Rydberg-dissociation spectroscopy. Analytical potential-energy functions of the X, A, and B states were derived using a global model of these states that includes the spin-orbit interaction. The observation of the highest vibrational levels of the B state and the onset of the Kr + Mg(3p) dissociation continuum enabled the precise determination of the dissociation energies of the X, A and B states of MgKr and of the a state of MgKr. The X, A and B states of MgKr are important stepping stones to access the Rydberg states of MgKr and the ground state of MgKr by resonant multiphoton excitation.

Non-stoichiometric magnetite as catalyst for the photocatalytic degradation of phenol and 2,6-dibromo-4-methylphenol - a new approach in water treatment.

Phenol and 2,6-dibromo-4-methylphenol (DBMP) were removed from aqueous solutions by ozonolysis and photocatalysis. The properties and structural features of the catalysts and the organic compounds are discussed, as well as their influence on the degradation reaction rates. The degradation efficiency in photocatalytic processes was higher for DBMP (98%) than for phenol (approximately 50%). This proves the high efficiency of magnetite in the photocatalytic degradation of halogenated aromatic pollutants. The particularly high degradation efficiency regarding halogen-containing DBMP molecules and the yield of bromide ions indicate that DBMP degradation follows a mixed reduction-oxidation mechanism. DBMP molecules interact with the magnetite surface, enabling them to react with the available electrons, and, as a result, bromide ions can be released. The results confirm that magnetite is an effective photocatalyst in the degradation of halogenated aromatic pollutants.

Direct, automated and sensitive determination of glyphosate and related anionic pesticides in environmental water samples using solid-phase extraction on-line combined with liquid chromatography tandem mass spectrometry

An automated procedure for the simultaneous determination of six anionic pesticides, including glyphosate (GLY) and its transformation product aminomethylphosphonic acid (AMPA), was developed and applied to the analysis of environmental water samples. The proposed method combines on-line concentration of water samples (0.160 mL), with compounds separation in an anion-exchange liquid chromatography (LC) column, followed by their selective determination by tandem mass spectrometry (MS/MS). The global procedure was completed in 25 min, providing limits of quantification (LOQs) between 5 ng L−1 and 20 ng L−1, with reduced effect of the surface water matrix in the efficiency of process (SPE and ionization yields). The method was applied to the analysis of grab samples obtained from three watersheds, in two rural and one residential area, in Galicia (Northwest Spain). Out of six investigated compounds, Fosetyl, AMPA and GLY were noticed in the set of processed samples. Their detection frequencies increased from 12% (Fosetyl) to 88% (AMPA). Median concentrations followed the same trend varying from 9 ng L−1 (Fosetyl) to 44 ng L−1 (AMPA). The higher levels and the large seasonal variations in the residues of the latter species were noticed in small rivers affected by discharges of municipal sewage treatment plants (STPs).

Study of the dependence of light ion sputtering yields of carbon-modified surface titanium layers on their thickness

A theoretical sputtering model based on two mechanisms is used in this work to investigate the dependence of light ion sputtering yields of carbon-modified surface titanium layers on their thickness. The model used allows not only to correctly describe the nonlinear dependence of the sputtering yields on the layer thickness, but also to analyze the resulting dependencies. Calculations of the total sputtering yields of helium and hydrogen ions of surface layers of titanium modified with carbon are given in comparison with the results of computer simulations.

The CO2 profile and analytical model for the Pioneer Venus Large Probe neutral mass spectrometer

We present a significantly updated CO2 altitude profile for Venus (64.2–0.9 km) and provide support for a potential deep lower atmospheric haze of particles (≤17 km). We extracted this information by developing a new analytical model for mass spectra obtained by the Pioneer Venus Large Probe (PVLP) Neutral Mass Spectrometer (LNMS). Our model accounts for changes in LNMS configuration and output during descent and enables the disentanglement of isobaric species via a data fitting routine that adjusts for mass-dependent changes in peak shape. The model yields CO2 in units of density (kg m−3), isotope ratios for 13C/12C and 18O/16O, and 14 measures of CO2 density across 55.4–0.9 km, which represents the most complete altitude profile for CO2 at ≤60 km to date. The CO2 density profile is also consistent with the pressure, temperature, and volumetric gas measurements from the PVLP and VeNeRa spacecraft. Nominal and low-noise operations for the LNMS mass analyzer are supported by the behaviors (e.g., ionization yields, fragmentation yields, and peak shapes) of several internal standards (e.g., CH3+, CH4+, 40Ar+, 136Xe2+, and 136Xe+), which were tracked across the descent. Lastly, our review of the CO2 profile and LNMS spectra reveals hitherto unreported partial and rapidly clearing clogs of the inlet in the lower atmosphere, along with several ensuing data spikes at multiple masses. Together, these observations suggest that atmospheric intake was impacted by particles at ≤17 km and that rapid particle degradation at the inlet yielded a temporary influx of mass signals into the LNMS.

Cationization of organic molecules under keV and MeV primary ion bombardment

The present work reports on cationization characteristics of organic molecules in alkali metal environment. Samples of arginine and polyethylene glycol polymers with average masses of 600, 1000 and 1500 were mixed with sodium- and potassium trifluoroacetate of various concentrations, and analyzed through secondary ion mass spectrometry. Bombardment proceeded with ions within both keV and MeV energy domains. Added salts positively affected the secondary ion yield through attachment of Na or K to organic molecule. Ionization differences between swift (MeV) ions and cluster ions, commonly used for secondary ion mass spectrometry analysis, were studied for arginine and PEG 600. While for arginine, secondary ion yield enhancement was only by a factor of 2, when analysing with MeV ions, and no enhancement was observed with keV Bi3 clusters, all polyethylene glycol samples showed increase of the secondary ion yield by factors between 3 and 40, depending on the amount of potassium or sodium that was mixed into the matrix. Additionally, higher amounts of salts also resulted in decreased fragmentation probability for organic molecules, reducing the intensities of specific fragments by more than two orders of magnitude.

All-electron, density-functional-based method for angle-resolved tunneling ionization in the adiabatic regime

We develop and test a method that integrates many-electron weak-field asymptotic theory (ME-WFAT) [Phys. Rev. A 89, 013421 (2014)] in the integral representation (IR) into the density functional theory (DFT) framework. In particular, we present modifications of the integral formula in the IR ME-WFAT to incorporate the potential terms unique to DFT. By solving an adiabatic rate equation for the angle-resolved ionization yield in our DFT-based ME-WFAT method, we show that the results are in excellent agreement with those of real-time time-dependent density functional theory (RT-TDDFT) simulations for NO, OCS, CH$_3$Br, and CH$_3$Cl interacting with one- and two- color laser fields with a fundamental wavelength of $800$ nm. This agreement is significant because the WFAT calculations take only a small fraction of the time of full TDDFT calculations. These results suggest that in the wavelength region commonly used in strong-field experiments ($800$ nm and longer), our DFT-based WFAT treatment can be used to rapidly screen for the ionization properties of a large number of molecules as a function of alignment or orientation between the molecule and the strong field.

Quantitative Identification of Nonpolar Perfluoroalkyl Substances by Mass Spectrometry.

Identifying and quantifying mixtures of compounds with very similar fragmentation patterns in their mass spectra presents a unique and challenging problem. In particular, the mass spectra of most per- and poly-fluoroalkyl substances (PFAS) lack a molecular ion. This complicates their identification, especially when using the absence of chromatographic separation. Here, we focus on linear, nonpolar, short-chain PFAS, which have received less attention than amphipathic PFAS despite their longer environmental lifetimes and greater global warming potentials. We identify and quantify n-C5F12 and n-C6F14 in binary mixtures by analyzing small changes in abundances of the main fragment ions following femtosecond tunnel laser ionization, without the need of chromatographic separation. Time-resolved femtosecond ionization mass spectrometry reveals that the metastable cation of both compounds undergoes predissociation within 1-2 ps of ion formation, with yields of C3F7+ showing evidence of coherent vibrational dynamics. These coherent oscillations are compared to low-level ion-state calculations and supported the idea that the oscillations in the C3F7+ ion yield are due to vibrations in the C5F12+• and C6F14+• radical cations and are associated with the predissociation dynamics of the metastable molecular ion. Surprisingly, we find that the fragment ions used for quantifying the mixtures have similar fragmentation dynamics. Conversely, the odd-electron C2F4+• fragment shows different time dependence between the two compounds, yet has negligible difference in the relative ion yield between the two compounds. Our findings indicate that femtosecond laser ionization may be a useful tool for identifying and quantifying mixtures of PFAS without the need of chromatography or high-resolution mass spectrometry.

Development of the caesium oven for HUST negative ion source

Caesium (Cs) will be evaporated inside the HUST negative ion source to enhance the negative ion yield by lowering the surface work function. To control the Cs vapour flux precisely, an advanced Cs oven with a temperature control system was developed. This paper introduces the design and construction of the Cs oven firstly. The Cs distribution and flux under different temperature conditions were analysed based on the Monte Carlo method, with the aim of providing an experimental reference. After manufacturing and assembly, Cs evaporation tests were successfully conducted and monitored using surface ionization detectors.

Detection of the amino acid histidine and its breakup products in hypervelocity impact ice spectra

Impact ionization time of flight mass spectrometry (TOF-MS) instruments study molecular composition of space-borne dust grains by impacting them at several km/s. The kinetic energy of the impact ionizes molecules from the dust grain, allowing them to be characterized with TOF-MS. The ability of these instruments to assess the inventory and distribution of organics throughout the solar system is important for understanding habitability across planetary bodies and the origins of terrestrial life. In particular, it would be beneficial to know whether this type of instrument can successfully detect amino acids, or other organics necessary for life that may be found on potentially habitable ocean worlds such as Europa. However, there have been questions about whether the fast impact ionization processes can shatter complex organic molecules before they can be studied, and if there is some critical flyby velocity below which fragmentation can be mitigated. Here we describe a set of experiments using a novel airbrushing technique for ice creation at the Colorado Dust Accelerator at the Institute for Modeling Plasmas, Atmospheres, and Cosmic Dust (IMPACT). Experiment 1 used a surface of pure histidine-monohydrochloride, and Experiment 2 used an identical histidine sample, except with a 60 nm water ice layer vapor deposited on top. These surfaces were kept at ∼80 Kelvin and impacted by <2μm-diameter iron dust particles at velocities ¿ 3 km/s. The resulting impact plumes were studied using TOF-MS, and the ion yields of fragmentation products relative to the parent molecule were measured. Direct comparison of the breakup products for each experiment show that water ice layers significantly reduce fragmentation rates, both in absolute terms and as functions of velocity. We find that for the bare amino acid, the fragmentation rate rises significantly beyond 6.1 km/s, while the ice-shielded amino acid shows significant increases beyond 8.5 km/s. Furthermore, observed fragmentation species correlate with those produced by published results from electron ionization experiments. In particular, we observe characteristic breakup products for histidine at masses 81–83 and 110 AMU, the dominant breakup products associated with histidine in the existing literature.

Strong-field ionization of N2 and CO molecules using two-color laser field

Two-color strong-field photoionization of two diatomic molecules (N2, CO) is studied using a velocity map imaging (VMI) spectrometer. The fundamental frequency, along with the second harmonic (800 + 400 nm) at different phases, with the two different polarization schemes viz, orthogonal and parallel, is employed for measuring the ion yields and photoelectron momentum distributions. The yield of the parent ion and its charged fragments as a function of the phase difference between the two-color field has been studied thoroughly, and the results are presented here. The correlation trends of the parent ion with their fragments as a function of the relative phase are discussed. It is observed that the ionized CO and its fragments have different correlation trends at different polarization schemes. Additionally, the photoelectron momentum distribution of N2 and CO due to orthogonal two-color (OTC) and parallel two-color (PTC) is performed in order to understand the modulation of electron dynamics as a function of phase between 800 nm and 400 nm. Further, the asymmetry parameter as a function of electron momenta due to the two-color fields has been estimated and discussed.

Atomic-structure investigations of neutral einsteinium by laser resonance ionization

Excited atomic states of neutral einsteinium were investigated by resonant laser ionization using 10 pg $(2\ifmmode\times\else\texttimes\fi{}{10}^{10}$ atoms) of $^{254}\mathrm{Es}$. Ten transitions from the ${5f}^{11}7s{}^{2}^{4}I_{15/2}^{o}$ ground state to even-parity states were investigated in detail, via studies of lifetimes and further excitation steps into higher-lying odd-parity states below and above the first ionization potential. This led to the identification of 37 previously unknown odd-parity energy levels in the region between $37\phantom{\rule{0.16em}{0ex}}000$ and $42\phantom{\rule{0.16em}{0ex}}500\phantom{\rule{0.16em}{0ex}}\mathrm{cm}{}^{\ensuremath{-}1}$ and a number of autoionizing states, which ensure a high ion yield in resonant ionization. Rydberg states were identified and the corresponding Rydberg series converging either to the ionic ground or an excited state were analyzed to determine the first ionization potential of einsteinium to a value of ${E}_{\text{IP}}=51\phantom{\rule{0.16em}{0ex}}364.58{(14)}_{\mathrm{stat}}{(50)}_{\mathrm{sys}}\phantom{\rule{0.16em}{0ex}}\mathrm{cm}{}^{\ensuremath{-}1}$, improving the previous result by a factor of four.

Numerical studies of isotopic selective photoionization of ytterbium in a three-step ionization scheme

Selective photoionization of ytterbium isotope is studied numerically based on a three-step photoionization scheme, 4f146s2 1S0 (0 cm−1) → 4f146s6p 3P1 (17992.008 cm−1) → (4f136s26p) (7/2, 3/2)2 (35196.98 cm−1) → auto-ionization state (52353 cm−1) → Yb+, by the density matrix theory with the consideration of atomic hyperfine structures and magnetic sublevels. To examine the physical model, the numerical isotopic abundance of ytterbium is compared with that from mass spectroscopy experiment, showing that they are in good agreement with each other. The excitation process and ionization process of ytterbium, especially for odd isotopes, are discussed and analyzed in detail on this basis. The effects of frequency detuning, power densities, spectral bandwidths, polarization of two excitation lasers, and atomic Doppler broadening on the total ionization yield and isotopic abundance are investigated numerically and the optimal excitation conditions for 176Yb enrichment are identified semi-quantitatively.