Nitrogen Buffer Gas Research Articles

Picotesla optically pumped magnetometer using a laser-written vapor cell with sub-mm cross section

We demonstrate a sensitive optically pumped magnetometer using rubidium vapor and 0.75 amg of nitrogen buffer gas in a sub-mm-width sensing channel excavated by femtosecond laser writing followed by chemical etching. The channel is buried less than 1 mm below the surface of its fused silica host material, which also includes reservoir chambers and micro-strainer connections, to preserve a clean optical environment. Using a zero-field-resonance magnetometry strategy and a sensing volume of 2.25 mm3, we demonstrate a sensitivity of ≈1pT/Hz at 10 Hz. The device can be integrated with photonic structures and microfluidic channels with 3D versatility. Its sensitivity, bandwidth, and stand-off distance will enable detection of localized fields from magnetic nanoparticles and μL NMR samples.

Ion-molecule collision cross-section calculations using trajectory parallelization in distributed systems

Ion Mobility coupled with Mass Spectrometry (IM-MS) stands as a strong analytical method for structurally characterizing complex molecules. In IM-MS, the sample under investigation is ionized and propelled by an electric field into a drift tube, which collides against a buffer gas. The separation of the ion gas phase is then measured through the differences in their rotationally averaged Collision Cross-Section (CCS) values. The effectiveness of the measured Collision Cross-Section (CCS) for structural characterization critically depends on the validation against theoretical calculations. This validation process relies on intensive molecular mechanics simulations, which can be computationally demanding, especially for large systems such as molecular assemblies and viruses. Therefore, reliable and fast CCS calculations are needed to help interpret IM-MS experimental data. This work presents the MassCCS software, which considerably increases the CCS simulation performance by implementing a linked-cell-based algorithm, incorporating High-Performance Computing (HPC) techniques. We performed extensive tests regarding the system size, shape, and number of CPU cores. Experimental results reveal speedups up to 3 orders of magnitude faster than Collision Simulator for Ion Mobility Spectrometry (CoSIMS) and High-Performance Collision Cross Section (HPCCS), optimized solutions for CCS simulations, for a single node execution. In addition, we extended MassCCS at the inter-node level by employing OpenMP Cluster (OMPC). OMPC is an innovative programming model designed for the development of HPC applications. It streamlines the development process and simplifies software maintenance using only OpenMP directives. Notably, OMPC delivers a performance level comparable to a pure MPI implementation. This enhancement enabled expensive CCS calculations using nitrogen buffer gas for large systems such as human adenovirus with ∼11 million atoms in just ∼4 min, making MassCCS the most performant software nowadays, to the best of our knowledge. MassCCS is available as free software for Academic use at https://github.com/cces-cepid/massccs.

Free-induction-decay magnetic field imaging with a microfabricated Cs vapor cell.

Magnetic field imaging is a valuable resource for signal source localization and characterization. This work reports an optically pumped magnetometer (OPM) based on the free-induction-decay (FID) protocol, that implements microfabricated cesium (Cs) vapor cell technology to visualize the magnetic field distributions resulting from various magnetic sources placed close to the cell. The slow diffusion of Cs atoms in the presence of a nitrogen (N2) buffer gas enables spatially independent measurements to be made within the same vapor cell by translating a 175 μm diameter probe beam over the sensing area. For example, the OPM was used to record temporal and spatial information to reconstruct magnetic field distributions in one and two dimensions. The optimal magnetometer sensitivity was estimated to be 0.43 pT/H z within a Nyquist limited bandwidth of 500 Hz. Furthermore, the sensor's dynamic range exceeds the Earth's field of approximately 50 μT, which provides a framework for magnetic field imaging in unshielded environments.

Nitrogen buffer gas pressure tuning in a micro-machined vapor cell

We demonstrate a controllable depletion of the nitrogen buffer gas pressure in a micro-machined cesium (Cs) vapor cell from the dynamic heating of an alkali dispenser pill. When the alkali source is laser activated, the gettering compounds within the alkali pill dispenser reduce the nitrogen (N2) content from the vapor for fine-tuning of the alkali to buffer gas pressure ratio, with a demonstrated pressure step size as low as 1 Torr. Additionally, we decrease the buffer gas pressure below 100 mTorr to evaluate the presence of other potential broadening mechanisms. Real-time control of the gas pressure ratio in the vapor cell will have notable benefits for refining atomic sensor performance and provide a routine to achieve various target pressures across a wafer bonded with a uniform back-filled buffer gas pressure.

An improved source of spin-polarized electrons based on spin exchange in optically pumped rubidium vapor

We have improved a polarized electron source in which unpolarized electrons undergo collisions with a mixture of buffer gas molecules and optically spin-polarized Rb atoms. With a nitrogen buffer gas, the source reliably provides spin polarization between 15% and 25% with beam currents >4 μA. Vacuum pump upgrades mitigate problems caused by denatured diffusion pump oil, leading to longer run times. A new differential pumping scheme allows the use of higher buffer gas pressures up to 800 mTorr. With a new optics layout, the Rb polarization is continuously monitored by a probe laser and improved pump laser power provides more constant high polarization. We have implemented an einzel lens to better control the energy of the electrons delivered to the target chamber and to preferentially select electron populations of higher polarization. The source is designed for studies of biologically relevant chiral molecule samples, which can poison photoemission-based GaAs polarized electron sources at very low partial pressures. It operates adjacent to a target chamber that rises to pressures as high as 10−4 Torr and has been implemented in a first experiment with chiral cysteine targets.

Alignment-Based Optically Pumped Magnetometer Using a Buffer-Gas Cell

Alignment-based optically pumped magnetometers (OPMs) are capable of measuring oscillating magnetic fields with high sensitivity in the $\mathrm{fT}/\sqrt{\mathrm{Hz}}$ range. Until now, alignment-based magnetometers have only used paraffin-coated vapour cells to extend the spin relaxation lifetimes of the alkali vapour. The drawback of these cells is that they are hand blown and are therefore time intensive, and somewhat unreliable, to produce. Buffer-gas cells, on the other hand, can be manufactured on a mass scale using microfabrication techniques. In this work we use hand-blown cells, but our methods also apply to microfabricated buffer-gas cells. We present the first demonstration of an alignment-based magnetometer using a buffer-gas vapour cell containing caesium (Cs) alkali vapour and nitrogen (${\mathrm{N}}_{2}$) buffer gas. The OPM is operated at $55{\phantom{\rule{0.1em}{0ex}}}^{\ensuremath{\circ}}\mathrm{C}$ and we achieve a $325\phantom{\rule{0.2em}{0ex}}\mathrm{fT}/\sqrt{\mathrm{Hz}}$ sensitivity to 10 kHz oscillating magnetic fields with an 800 Hz bandwidth. The alignment-based magnetometer uses a single low-power laser beam for optical pumping and probing and could potentially allow for more rapid commercialization of radio-frequency OPMs, due to the robustness of the one-beam geometry.

A study of the sign reversal from a transmission peak to an absorption dip in a V-type system using the D1 and D2 lines of 87Rb in the presence of a buffer gas

In this work, we have investigated the transmission peak and absorption dip in the Doppler broadened V-type system using the D1 and D2 lines of 87Rb atoms in the presence of nitrogen buffer gas. The effects of the probe power variations at a fixed pump power on these resonances are examined both experimentally and theoretically. We have explored the fact that the transmission peak essentially turns into an absorption dip when the probe power is stronger than the pump power. Moreover, the theoretical model of a five-level V-type system is found to be sufficient to support the experimental outcomes when the effect of collision due to the presence of buffer gas is included in the theoretical model. We have also shown the variation of the resonance amplitude and population distribution in the upper level (|5〉) with increasing probe power.

Quantitation of Enantiomeric Excess in an Achiral Environment Using Trapped Ion Mobility Mass Spectrometry.

We present a novel, straightforward method to determine the enantiomeric excess (ee) of tryptophan (Trp) and N-tert-butyloxycarbonyl-O-benzylserine (BBS) solutions without chiral additives. For this, lithium carbonate, sodium carbonate, or silver acetate was added to solutions of Trp or BBS. Singly negatively charged dimer and trimer clusters were then formed by electrospray ionization and analyzed using trapped ion mobility spectrometry (TIMS) and time-of-flight mass spectrometry. When a solution contains both enantiomers, homo- and heterochiral clusters are generated which can be separated in the TIMS-tunnel based on their different mobilities using a nitrogen buffer gas. The ratio of homochiral to heterochiral clusters shows a binomial distribution and can be calibrated with solutions of known ee to yield ee measurements of samples with better than 1% accuracy. Samples can be prepared rapidly, and measurements are completed in less than 5 min. Current instrumental limitations restrict this method to rigid molecules with large functional groups adjacent to the chiral centers. Nevertheless, we expect this method to be applicable to many pharmaceuticals and provide the example of 1-methyltryptophan to demonstrate this.

Evaluating the Effects of Metal Adduction and Charge Isomerism on Ion-Mobility Measurements using m-Xylene Macrocycles as Models.

Gas-phase ion-mobility spectrometry provides a unique platform to study the effect of mobile charge(s) or charge location on collisional cross section and ion separation. Here, we evaluate the effects of cation/anion adduction in a series of xylene and pyridyl macrocycles that contain ureas and thioureas. We explore how zinc binding led to unexpected deprotonation of the thiourea macrocyclic host in positive polarity ionization and subsequently how charge isomerism due to cation (zinc metal) and anion (chloride counterion) adduction or proton competition among acceptors can affect the measured collisional cross sections in helium and nitrogen buffer gases. Our approach uses synthetic chemistry to design macrocycle targets and a combination of ion-mobility spectrometry mass spectrometry experiments and quantum mechanics calculations to characterize their structural properties. We demonstrate that charge isomerism significantly improves ion-mobility resolution and allows for determination of the metal binding mechanism in metal-inclusion macrocyclic complexes. Additionally, charge isomers can be populated in molecules where individual protons are shared between acceptors. In these cases, interactions via drift gas collisions magnify the conformational differences. Finally, for the macrocyclic systems we report here, charge isomers are observed in both helium and nitrogen drift gases with similar resolution. The separation factor does not simply increase with increasing drift gas polarizability. Our study sheds light on important properties of charge isomerism and offers strategies to take advantage of this phenomenon in analytical separations.

Ppb level detection of carbonyl sulfide and ethene and study resonant frequencies using laser photoacoustic spectroscopy

AbstractLaser photoacoustic spectroscopy is a laser measurement method with high sensitivity, good selectivity, nondestructive, and fast response (real‐time). In the present work, to detect carbonyl sulfide and ethene gases and measure resonant frequencies and signals, the photoacoustic spectroscopy system was designed and set up. The detection limit of this system to trace ethene and carbonyl sulfide was measured 3 ppb and 8 ppb, respectively. Also, for these two gases at the presence of different buffer gases, the resonant frequency and photoacoustic signal were recorded. The results showed that among the used buffer gases, xenon has the best acoustic performance and gives the highest photoacoustic signal. The signal also increased with increasing pressure of buffer gas, because increasing the pressure leads to improved collisional processes. The study of resonant frequencies of this system for these two gases in the presence of buffer gases showed that with increasing the pressure of xenon, argon, and nitrogen buffer gases from 65 to 765 Torr, the resonant frequency does not change significantly. But in the case of helium buffer gas, these resonant frequency changes are significant, and as the helium pressure increases by 65 to 765 Torr, the resonant frequencies of carbonyl sulfide and ethene change from 2016 to 2630 Hz and from 2100 to 2740 Hz, respectively. The reason for the different behavior of helium is the higher speed of sound in helium than in other buffer gases.

High resolution emission FT spectra of sodium in a microwave discharge: Intensity variation of the D[formula omitted]/D[formula omitted] lines in exoplanetary atmospheres

The intensity ratio of the D1 and D2 sodium-doublet emission lines varies both across spectra of astronomical sources and in laboratory plasmala. This article probes the behaviour of this ratio under controlled laboratory conditions. In order to study this variation, we have recorded microwave discharge spectra of sodium vapour in range of 15000 to 18000 cm−1. Emission bands of the molecular nitrogen buffer gas and kinetic broadening of nitrogen and sodium lines have been used in a characterisation of the discharge temperature. We show that the relative intensity of doublet lines is determined by self-absorption and depends on the buffer-gas pressure and discharge power. The ratio and line shapes can be explained by a two-temperature model of sodium emission and foreground absorption. Line ratios estimated for spectra with various strength of the self-absorption of electric discharges can be used for characterising their temperatures and densities. In contemporary astronomical observation of exoplanetary atmospheres, this effect has not been resolved yet. To observe this effect, at least 0.01 - 0.05 cm−1 resolution (resolving power 1 600 000) is required. We make a connection to stellar Na emission and possible absorption processes for future observations of exoplanetary atmospheres.

Assessing Collision Cross Section Calibration Strategies for Traveling Wave-Based Ion Mobility Separations in Structures for Lossless Ion Manipulations.

The collision cross section (CCS) is an important property that aids in the structural characterization of molecules. Here, we investigated the CCS calibration accuracy with traveling wave ion mobility spectrometry (TWIMS) separations in structures for lossless ion manipulations (SLIM) using three sets of calibrants. A series of singly negatively charged phospholipids and bile acids were calibrated in nitrogen buffer gas using two different TW waveform profiles (square and sine) and amplitudes (20, 25, and 30 V0-p). The calibration errors for the three calibrant sets (Agilent tuning mixture, polyalanine, and one assembled in-house) showed negligible differences using a sine-shaped TW waveform. Calibration errors were all within 1-2% of the drift tube ion mobility spectrometry (DTIMS) measurements, with lower errors for sine waveforms, presumably due to the lower average and maximum fields experienced by ions. Finally, ultrahigh-resolution multipass (long path length) SLIM TWIMS separations demonstrated improved CCS calibration for phospholipid and bile acid isomers.

Photodetachment and photoreactions of substituted naphthalene anions in a tandem ion mobility spectrometer.

Substituted naphthalene anions (deprotonated 2-naphthol and 6-hydroxy-2-naphthoic acid) are spectroscopically probed in a tandem drift tube ion mobility spectrometer (IMS). Target anions are selected according to their drift speed through nitrogen buffer gas in the first IMS stage before being exposed to a pulse of tunable light that induces either photodissociation or electron photodetachment, which is conveniently monitored by scavenging the detached electrons with trace SF6 in the buffer gas. The photodetachment action spectrum of the 2-naphtholate anion exhibits a band system spanning 380-460 nm with a prominent series of peaks spaced by 440 cm-1, commencing at 458.5 nm, and a set of weaker peaks near the electron detachment threshold corresponding to transitions to dipole-bound states. The two deprotomers of 6-hydroxy-2-naphthoic acid are separated and spectroscopically probed independently. The molecular anion formed from deprotonation of the hydroxy group gives rise to a photodetachment action spectrum similar to that of the 2-naphtholate anion with an onset at 470 nm and a maximum at 420 nm. Near the threshold, the photoreaction with SF6 is observed with displacement of an OH group by an F atom. In contrast, the anion formed from deprotonation of the carboxylic acid group gives rise to a photodissociation action spectrum, recorded on the CO2 loss channel, lying at much shorter wavelengths with an onset at 360 nm and maximum photoresponse at 325 nm.

Free-Induction-Decay Magnetometer Based on a Microfabricated Cs Vapor Cell

We describe an optically pumped Cs magnetometer containing a 1.5 mm thick microfabricated vapor cell with nitrogen buffer gas operating in a free-induction-decay (FID) configuration. This allows us to monitor the free Larmor precession of the spin coherent Cs atoms by separating the pump and probe phases in the time domain. A single light pulse can sufficiently polarize the atomic sample however, synchronous modulation of the light field actively drives the precession and maximizes the induced spin coherence. Both amplitude and frequency modulation have been implemented with noise floors of 3 pT / √ Hz and 16 pT / √ Hz respectively within the Nyquist limited bandwidth of 500 Hz .

Exploring the Complexity of Steviol Glycosides Analysis Using Ion Mobility Mass Spectrometry.

A proof of principle method using ion mobility-mass spectrometry (IM-MS) and collision induced dissociation (CID) coupled with micro flow ultra high-performance chromatography (UHPLC-IM-MS) has been developed to screen for steviol glycosides. Traveling wave ion mobility was used to determine rotationally averaged collision cross sections in nitrogen buffer gas (TWCCSN2). To explore the evolving applicability of ion mobility screening, the analytical approach was initially developed and applied to the analysis of a steviol/steviol glycoside spiked chocolate spread extract. Subsequently 55 food commodities were screened using a steviol glycoside TWCCSN2 library. IM analyses produced TWCCSN2 values, enabling the unequivocal identification of the steviol glycosides and isomeric pairs (negating the reliance on product ions). In addition, coeluting isomeric species, comprising (labile fragment ions, doubly charged dimers, and multiply charged species) have been identified and resolved. Isomeric false detections were avoided, with the coeluting isomeric species quantified. A quantitative assessment of TWCCSN2 in the analysis of steviol glycosides was performed.

Anisotropic Etching of Hexagonal Boron Nitride and Graphene: Question of Edge Terminations.

Chemical vapor deposition (CVD) has been established as the most effective way to grow large area two-dimensional materials. Direct study of the etching process can reveal subtleties of this competing with the growth reaction and thus provide the necessary details of the overall growth mechanism. Here we investigate hydrogen-induced etching of hBN and graphene and compare the results with the classical kinetic Wulff construction model. Formation of the anisotropically etched holes in the center of hBN and graphene single crystals was observed along with the changes in the crystals' circumference. We show that the edges of triangular holes in hBN crystals formed at regular etching conditions are parallel to B-terminated zigzags, opposite to the N-terminated zigzag edges of hBN triangular crystals. The morphology of the etched hBN holes is affected by a disbalance of the B/N ratio upon etching and can be shifted toward the anticipated from the Wulff model N-terminated zigzag by etching in a nitrogen buffer gas instead of a typical argon. For graphene, etched hexagonal holes are terminated by zigzag, while the crystal circumference is gradually changing from a pure zigzag to a slanted angle resulting in dodecagons.

Optical spin noise spectra of Rb atomic gas with homogeneous and inhomogeneous broadening

We study the optical spin noise spectra of Rb atomic gas with different broadening mechanisms. The first is homogeneous broadening using 250 Torr nitrogen buffer gas, while the other mechanism is inhomogeneous broadening via the Doppler effect without buffer gas. Spin noise signals are measured by the typical spin noise spectroscopy geometry (single-pass geometry) and the saturated absorption spectroscopy geometry (double-pass geometry). In the homogeneously broadened system, the line shape of the optical spin noise spectra shows a pronounced dip that vanishes at the center of the band in both geometries. In the inhomogeneously broadened system, however, a peak in the single-pass geometry and a dip in the double-pass geometry at the band center are observed. The difference between the optical spin noise spectra from these two systems arises from their different level-broadening mechanisms.

Development of a low-debris laser driven tape drive soft x-ray source

This paper focuses on debris mitigation in a laser driven tape drive x-ray source. A smart design is being used to minimise the effect of shockwave reflection from the target's back and a continuous rough pumping is utilised to obtain an efficient purging of big lumpy debris particles out of the interaction chamber. The effect of low pressure (3–6 mbar) nitrogen buffer gas is studied together with a moderate magnetic field (0.14 Tesla) on both debris spall and hot ions trajectory. The target material for this work is a 15 μm VHS video tape composed of Mylar as carrier film with Fe2O3 and CrO2 powder. The experiments were conducted using a long pulsed 800ps, 50 Hz Nd: YAG laser. The results obtained appeared to be promising in reducing the damaging effect of large debris particles (between 50 and 140 microns) as well as small particles (∼ 5 microns) that deteriorates the efficiency of delicate optics.

Molecular Structures and Momentum Transfer Cross Sections: The Influence of the Analyte Charge Distribution.

Structure elucidation by ion mobility spectrometry-mass spectrometry methods is based on the comparison of an experimentally measured momentum transfer cross-section to cross-sections calculated for model structures. Thus, it is imperative that the calculated cross-section must be accurate. However, it is not fully understood how important it is to accurately model the charge distribution of an analyte ion when calculating momentum transfer cross-sections. Here, we calculate and compare momentum transfer cross-sections for carbon clusters that differ in mass, charge state, and mode of charge distribution, and vary temperature and polarizability of the buffer gas. Our data indicate that the detailed distribution of the ion charge density is intimately linked to the contribution of glancing collisions to the momentum transfer cross-section. The data suggest that analyte ions with molecular mass ~3 kDa or momentum transfer cross-section 400-500 Å2 would be significantly influenced by the charge distribution in nitrogen buffer gas. Our data further suggest that accurate structure elucidation on the basis of IMS-MS data measured in nitrogen buffer gas must account for the molecular charge distribution even for systems as large as C960 (~12 kDa) when localized charges are present and/or measurements are conducted under cryogenic temperatures. Finally, our data underscore that accurate structure elucidation is unlikely if ion mobility data recorded in one buffer gas is converted into other buffer gases when electronic properties of the buffer gases differ. Graphical Abstract ᅟ.

Isomerisation of an intramolecular hydrogen-bonded photoswitch: protonated azobis(2-imidazole).

Photoisomerisation of protonated azobis(2-imidazole), an intramolecular hydrogen-bonded azoheteroarene photoswitch molecule, is investigated in the gas phase using tandem ion mobility mass spectrometry. The E and Z isomers exhibit distinct spectral responses, with E-Z photoisomerisation occurring over the 360-520 nm range (peak at 460 nm), and Z-E photoisomerisation taking place over the 320-420 nm range (peak at 390 nm). A minor photodissociation channel involving loss of N2 is observed for the E-isomer with a maximum efficiency at 390 nm, blue-shifted by ≈70 nm relative to the wavelength for maximum photoisomerisation response. Loss of N2 is also the predominant collision-induced dissociation channel. Electronic structure calculations suggest that E-isomer photoisomerisation involves S1(ππ*) excitation, whereas the Z-isomer photoisomerisation involves S2(ππ*) excitation. Conversion between the E and Z isomers through collisional excitation, which is calculated to occur through both inversion and torsion pathways, is investigated experimentally by colliding the molecular ions with nitrogen buffer gas over a range of electric fields. This study demonstrates the versatility of tandem ion mobility mass spectrometry for exploring the isomerisation of molecular photoswitches initiated by either light or collisions.