Neutral Buffer Gas Research Articles

Leak-Out Spectroscopy, A Universal Method of Action Spectroscopy in Cold Ion Traps.

A novel method of spectroscopy in ion traps termed leak-out spectroscopy (LOS) is presented. Here, mass-selected, cold ions are excited by an infrared laser. In a subsequent collision with a neutral buffer gas particle, their internal energy is then transferred to kinetic energy. As a result, these ions leak out from the ion trap and are detected. The LOS scheme is generally applicable, very sensitive, and close to background-free when operated at low temperature. The potential of this method is demonstrated and characterized here for the first time by recording the rotationally resolved spectrum of the C-H stretching vibration ν1 of linear C3H+. Besides performing high-resolution spectroscopy, this method opens up the way for analyzing the composition of trap content, for example, determining isomer ratios, by selectively expelling isomers or other isobaric ions from the trap. Likewise, LOS can be used to prepare clean samples of structural and nuclear spin isomers.

Applications of ion mobility-mass spectrometry in the chemical analysis in traditional Chinese medicines

离子淌度质谱(IM-MS)是一种将离子淌度分离与质谱分析相结合的新型分析技术。IM-MS的主要优势不仅是在质谱检测前提供了基于气相离子形状、大小、电荷数等因素的多一维分离,而且能够提供碰撞截面积、漂移时间等质谱信息进而辅助化合物鉴定。近年来,随着IM-MS技术的不断发展,该技术在中药化学成分分析中受到越来越多的关注。首先,IM-MS已成功应用于改善中药复杂成分尤其是同分异构体或等量异位素等成分的分离;其次,IM-MS可通过多重碎裂模式辅助高质量中药小分子质谱信息的获取;此外,IM-MS提供的高维质谱数据信息还可促进中药复杂体系多成分的整合分析。该文在对IM-MS分类和基本原理进行概述的基础上,从分离能力及分离策略、多重碎裂模式、多维质谱数据处理策略3个方面,重点综述了IM-MS在中药化学成分分析中的应用,以期为IM-MS在中药化学成分研究提供参考。

Breaking Down Structural Diversity for Comprehensive Prediction of Ion-Neutral Collision Cross Sections.

Identification of unknowns is a bottleneck for large-scale untargeted analyses like metabolomics or drug metabolite identification. Ion mobility-mass spectrometry (IM-MS) provides rapid two-dimensional separation of ions based on their mobility through a neutral buffer gas. The mobility of an ion is related to its collision cross section (CCS) with the buffer gas, a physical property that is determined by the size and shape of the ion. This structural dependency makes CCS a promising characteristic for compound identification, but this utility is limited by the availability of high-quality reference CCS values. CCS prediction using machine learning (ML) has recently shown promise in the field, but accurate and broadly applicable models are still lacking. Here we present a novel ML approach that employs a comprehensive collection of CCS values covering a wide range of chemical space. Using this diverse database, we identified the structural characteristics, represented by molecular quantum numbers (MQNs), that contribute to variance in CCS and assessed the performance of a variety of ML algorithms in predicting CCS. We found that by breaking down the chemical structural diversity using unsupervised clustering based on the MQNs, specific and accurate prediction models for each cluster can be trained, which showed superior performance than a single model trained with all data. Using this approach, we have robustly trained and characterized a CCS prediction model with high accuracy on diverse chemical structures. An all-in-one web interface (https://CCSbase.net) was built for querying the CCS database and accessing the predictive model to support unknown compound identifications.

Making ions cooler

Cooling of trapped ions with a neutral buffer gas makes the study of atom–ion hybrid systems possible in the quantum regime. The new record low achieved opens the door to numerous opportunities, including full control over the atom–ion interactions.

The energy distribution of an ion in a radiofrequency trap interacting with a nonuniform neutral buffer gas

An ion in a radiofrequency (rf) trap sympathetically cooled by a simultaneously trapped neutral buffer gas exhibits deviations from thermal statistics caused by collision-induced coupling of the rf field to the ion motion. For a uniform density distribution of the buffer gas, the energy distribution of the ion can be described by Tsallis statistics. Moreover, runaway heating of the ion occurs if the buffer gas particles are sufficiently heavy relative to the ion. In typical experiments, however, ultracold buffer gases are confined in traps resulting in localised, non-uniform density distributions. Using a superstatistical approach, we develop an analytical model for an ion interacting with a localised buffer gas. We demonstrate theoretically that limiting collisions to the centre of the ion trap enables cooling at far greater mass ratios than achievable using a uniform buffer gas, but that an upper limit to the usable mass ratio exists even in this case. Furthermore, we analytically derive the functional form of the energy distribution for an ion interacting with a buffer gas held in a harmonic potential. The analytical distribution obtained is found to be in excellent agreement with the results of numerical simulations.

Analysis of macroparticle charge screening in a nonequilibrium plasma based on the kinetic collisional point sink model

The screening of macroparticles in a nonequilibrium plasma is considered on the basis of the Vlasov kinetic equations supplemented with the collisional term in the Bhatnagar–Gross–Krook approximation and the point sink method. In this method, the absorption of electrons and ions by a macroparticle is described by introducing effective point sinks into the kinetic equations for plasma electrons and ions. Explicit expressions are derived for the potential distribution around a macroparticle and effective charges that determine the behavior of the potential at large distances taking into account collisions of electrons and ions with neutral buffer gas atoms. We consider the cases of a constant collision frequency and constant mean free paths of electrons and ions in the buffer gas. Numerical calculations are performed for dusty isothermal and nonisothermal plasmas in helium, neon, argon, krypton, and xenon at pressures of 10–1 to 104 Pa, which are typical of experiments with dusty plasmas.

Dynamics of a single trapped ion immersed in a buffer gas

We provide a comprehensive theoretical framework for describing the dynamics of a single trapped ion interacting with a neutral buffer gas, thus extending our previous studies on buffer-gas cooling of ions beyond the critical mass ratio [B. H\"oltkemeier et al., Phys. Rev. Lett. 116, 233003 (2016)]. By transforming the collisional processes into a frame, where the ion's micromotion is assigned to the buffer gas atoms, our model allows one to investigate the influence of non-homogeneous buffer gas configurations as well as higher multipole orders of the radio-frequency trap in great detail. Depending on the neutral-to-ion mass ratio, three regimes of sympathetic cooling are identified which are characterized by the form of the ion's energy distribution in equilibrium. We provide analytic expressions and numerical simulations of the ion's energy distribution, spatial profile and cooling rates for these different regimes. Based on these findings, a method for actively decreasing the ion's energy by reducing the spatial expansion of the buffer gas arises (Forced Sympathetic Cooling).

Neutral gas sympathetic cooling of an ion in a Paul trap.

A single ion immersed in a neutral buffer gas is studied. An analytical model is developed that gives a complete description of the dynamics and steady-state properties of the ions. An extension of this model, using techniques employed in the mathematics of economics and finance, is used to explain the recent observation of non-Maxwellian statistics for these systems. Taken together, these results offer an explanation of the long-standing issues associated with sympathetic cooling of an ion by a neutral buffer gas.

Structural Characterization of Drug-like Compounds by Ion Mobility Mass Spectrometry: Comparison of Theoretical and Experimentally Derived Nitrogen Collision Cross Sections

We present the use of drug-like molecules as a traveling wave (T-wave) ion mobility (IM) calibration sample set, covering the m/z range of 122.1-609.3, the nitrogen collision cross-section (Ω(N(2))) range of 124.5-254.3 Å(2) and the helium collision cross-section (Ω(He)) range of 63.0-178.8 Å(2). Absolute Ω(N(2)) and Ω(He) values for the drug-like calibrants and two diastereomers were measured using a drift-tube instrument with radio frequency (RF) ion confinement. T-wave drift-times for the protonated diastereomers betamethasone and dexamethasone are reproducibly different. Calibration of these drift-times yields T-wave Ω(N(2)) values of 189.4 and 190.4 Å(2), respectively. These results demonstrate the ability of T-wave IM spectrometry to differentiate diastereomers differing in Ω(N(2)) value by only 1 Å(2), even though the resolution of these IM experiments were ∼40 (Ω/ΔΩ). Demonstrated through density functional theory optimized geometries and ionic electrostatic surface potential analysis, the small but measurable mobility difference between the two diastereomers is mainly due to short-range van der Waals interactions with the neutral buffer gas and not long-range charge-induced dipole interactions. The experimental RF-confining drift-tube and T-wave Ω(N(2)) values were also evaluated using a nitrogen based trajectory method, optimized for T-wave operating temperature and pressures, incorporating additional scaling factors to the Lennard-Jones potentials. Experimental Ω(He) values were also compared to the original and optimized helium based trajectory methods.

3DCylPIC—A 3D particle-in-cell code in cylindrical coordinates for space charge simulations of ion trap and ion transport devices

Abstract A 3D particle-in-cell code in cylindrical coordinates, that can be used to characterize space charge effects in various ion traps and ion transport devices where cylindrical boundary conditions are more appropriate, is presented. By solving Poisson’s equation on a cylindrical grid at every time step, the presence of an arbitrary amount of charged particles is handled in a completely natural way. Hard sphere scattering and statistical diffusion models can be used to include effects of interaction with a neutral buffer gas. An overview of the code is discussed, and its first application to study RF carpet devices is presented.

Gas-phase ion dynamics in a periodic-focusing DC ion guide

In this work, we provide a comprehensive understanding of the radial ion focusing mechanism in the periodic-focusing DC ion guide (PDC IG). The PDC IG was developed in our laboratory to improve the sensitivity and throughput of ion mobility spectrometry (IMS) with respect to conventional uniform field IMS. Radial ion focusing, which is responsible for the sensitivity improvement, is attributed to the presence of effective potentials created by the fringing electric fields of thick ring electrodes and collisional cooling of the ions with the neutral buffer gas. The ion focusing mechanism is affirmed by investigating the variations in the effective ion temperature ( T eff ) which are dependent upon axial position in the device. The concepts derived herein outline guidelines for the design of high performance PDC IG ion mobility instruments and other ion optical devices such as periodic-focusing DC ion funnels.

A setup for measurements of free-electron lifetime in a gas phase

A setup for measuring the lifetime of free electrons in a neutral buffer gas that contains an electronegative impurity is described. This setup is intended for prompt diagnostics of carcinogenicity of chemical compounds and consists of an ionization chamber with laser photoionization of the cathode, a gas system, and a system for collection and processing of experimental data based on an HBJI45 amplitude-to-digital converter. The techniques for preparing the tested gaseous mixtures and processing the experimental results are described. The results of measurements of the lifetimes and calculated free-electron capture constants for a CO2 + O2 calibrating mixture and mixtures of CO2 with organic molecules are presented. The setup allows measurements of the lifetimes of free electrons in mixtures in the range 0.5–70 μs at measurement errors of 0.2–6%, respectively, and study of two or three potentially carcinogenic substances a week.

Ion debris characterization from a z-pinch extreme ultraviolet light source

An XTREME Technologies XTS 13-35 extreme ultraviolet (EUV) light source creates a xenon z pinch that generates 13.5nm light. Due to the near x-ray nature of light at this wavelength, extremely smooth metal mirrors for photon collection must be employed. These are exposed to the source debris. Dissolution of the z-pinch gas column results in high-energy ion and neutral release throughout the chamber that can have adverse effects on mirror surfaces. The XTREME commercial EUV emission diagnostic chamber was designed to maximize diagnostic access to the light and particulate emissions from the z pinch. The principal investigation is characterization of the debris field and the erosive effects on optics present. Light emission from the z pinch is followed by ejection of multiply charged ions and fast neutral particles that make up an erosive flux to chamber surfaces. Attenuation of this erosive flux to optical surfaces is attempted by inclusion of a debris mitigation tool consisting of foil traps and neutral buffer gas flow. Characterization of the z-pinch ejecta is performed with a spherical sector energy analyzer (ESA) that diagnoses fast ion species by energy-to-charge ratio using ion time-of-flight (ITOF) analysis. This is used to evaluate the debris tool’s ability to divert direct fast ions from impact on optic surfaces. The ITOF-ESA is used to characterize both the energy and angular distribution of the direct fast ions. Xe+ up to Xe+4 ions have been characterized along with Ar+ (the buffer gas used), W+, Mo+, Si+, Fe+, and Ni+. Energy spectra for these species from 0.5 up to 13keV are defined at 20° and 30° from the pinch centerline in the chamber. Results show a drop in ion flux with angular increase. The dominant species is Xe+ which peaks around 8keV. Ion flux measured against buffer gas flow rate suggests that the direct fast ion population is significantly attenuated through increases in buffer gas flow rate. This does not address momentum transfer from scattered ions or fast neutral particles. These results are discussed in the context of other investigations on the effects of total particle flux to normal incidence mirror samples exposed for 1×107 pulses. The samples (Si∕Mo multilayer with Ru capping layer, Au, C, Mo, Pd, Ru, and Si) were exposed to the source plasma with 75% argon flow rate in the debris mitigation tool and surface metrology was performed using x-ray photoelectron spectroscopy, atomic force microscopy, x-ray reflectivity, and scanning electron microscopy to analyze erosion effects on mirrors. These results are compared to the measured direct ion debris field.

Variable-temperature ion mobility time-of-flight mass spectrometry studies of electronic isomers of Kr2+ and CH3OH*+ radical cations.

Preliminary results from a liquid nitrogen-cooled ion mobility (IM) orthogonal-time-of-flight (o-ToF) mass spectrometer applied to the separation of electronic isomers of Kr2+ and methanol radical cations (conventional and distonic) are presented. Ab initio calculations were used to estimate the energies and energy barriers to interconversion between conventional (CH3OH*+) and distonic (CH2*OH2+) radical cations. In addition, computations and experiments are used to compare ion-neutral collision cross-sections for CH3OH*+ and CH2*OH2+ radical cations and suggest that the mobility separation is achieved by ion-neutral interactions between ions and neutral buffer gas.

Inward transport and compression of a positron plasma by a rotating electric field

Inward transport of a magnetized pure positron plasma confined in a Penning-Malmberg trap is produced by applying a rotating electric field to the plasma. Compression is observed over a broad range of frequencies. Compression factors up to 20 in central density were obtained. Positron collisions with a neutral buffer gas are used to counteract the heating due to the rotating electric field. The results have implications for a variety of applications including the production of brightness enhanced positron beams, the study of electron-positron plasmas, and antihydrogen production.

Gaussian basis functions in kinetic theory: I. Incorporation of inelastic processes

The dependence of the distribution functions for a gas mixture on the translational degrees of freedom is treated by means of superpositions of Gaussian distributions. The internal degrees of freedom of the gas molecules are taken into account by a Laplace transformation. After the general representation of the nonlinear collision operator an application is given, concerned with a simple version of drift-tube theory, i.e., the theory of a trace amount of ions moving in a neutral buffer gas under the influence of a strong homogeneous electric field.