Ion-shift reagent binding energy and the shift-mass correlation in ion mobility spectrometry

Ion mobility spectrometry is widely used for the detection of illegal substances and explosives in airports, ports, custom, some stations and many other important places. This task is usually complicated by false positives caused by overlapping the target peaks with that of interferents, commonly associated with samples of interest. Shift reagents (SR) are species that selectively change ion mobilities through adduction with analyte ions when they are introduced in IMS instruments. This characteristic can be used to discriminate false positives because the interferents and illegal substances respond differently to SR depending on the structure and size of analytes and their interaction energy with SR. This study demonstrates that ion mobility shifts upon introduction of SR depend, not only on the ion masses, but on the interaction energies of the ion:SR adducts. In this study, we introduced five different SRs using ESI-IMS-MS to study the effect of the interaction energy and size on mobility shifts. The mobility shifts showed a decreasing trend as the molecular weight increased for the series of compounds ethanolamine, valinol, serine, threonine, phenylalanine, tyrosine, tributylamine, tryptophan, desipramine, and tribenzylamine. It was proved that the decreasing trend was partially due to the inverse relation between the mobility and drift time and hence, the shift in drift time better reflects the pure effect of SR on the mobility of analytes. Yet the drift time shift exhibited a mild decrease with the mass of ions. Valinol pulled out from this trend because it had a low binding energy interaction with all the SR and, consequently, its clusters were short-lived. This short lifetime produced fewer collisions against the buffer gas and a drift time shorter compared to those of ions of similar molecular weight. Analyte ion:SR interactions were calculated using Gaussian. IMS with the introduction of SR could be the choice for the free-interferents detection of illegal drugs, explosives, and biological and warfare agents. The suppression of false positives could facilitate the transit of passengers and cargos, rise the confiscation of illicit substances, and save money and distresses due to needless delays. Keywords: Adduction, ion mobility spectrometry, mass spectrometry, shift reagent, valinol, buffer gas modifier

Real Time Flow Control System for Precise Gas Feed in COIL

This paper reports development of a real time flow control system for precise, controlled and uniform gas feed to a flowing medium Chemical Oxygen Iodine Laser (COIL). The optimal operation of this prominent laser depends upon the desired supply of gas constituents such as nitrogen (N2), chlorine (Cl2) and iodine (I2) to achieve adequately mixed laser gas. The laser also demands real time variation of flow rates during gas constituent transitions in order to maintain stabilized pressures in critical subsystems. Diluent nitrogen utilized for singlet oxygen transport is termed as primary buffer gas and that for iodine transport is termed as secondary buffer gas (with main and bypass components). Also, nitrogen in precise flows is used for mirror blowing, nozzle curtain, cavity bleed and diffuser startup. A compact hybrid data acquisition system (Hybrid DAS) for precise flow control using LabVIEW 2014 platform has been developed. The supported flow ranges may vary from few mmole.s-1 to few hundred mmole.s-1. The estimated relative uncertainty in the largest gas component i.e. primary buffer gas feed is nearly 0.7%. The implementation of in-operation variation using flow ramp enables swift stabilization of singlet oxygen generator pressures critical for successful COIL operation. The performance of Hybrid DAS is at par with fully wired DAS providing the crucial benefit of remote field operation at distances of nearly 80m in line of sight and 35m with obstacles

The Microfabricated Alkali Vapor Cell with High Hermeticity for Chip-Scale Atomic Clock

Herein, a microfabricated millimeter-level vapor alkali cell with a high hermeticity is fabricated through a wet etching and single-chip anodic bonding process. The vapor cell, containing Rb and N2, was investigated in a coherent population trapping (CPT) setup for the application of a chip-scale atomic clock (CSAC). The contrast of CPT resonance is up to 1.1% within the only 1 mm length of light interacting with atom. The effects of some critical external parameters on the CPT resonance, such as laser intensity, cell temperature, and buffer gas pressure, are thoroughly studied and optimized. The improved microfabricated vapor cell also exhibited great potential for other chip-scale atomic devices.

Transient electromagnetically induced transparency spectroscopy of 87Rb atom in buffer gas

We have studied the transient response dynamics of 87Rb atomic vapor buffered in 8 Torr Ne gas through an electromagnetically induced transparency configured in Λ-scheme. Experimentally, the temporal transmission spectra versus probe detuning by switching on and off the coupling one show complex structures. The transmitted probe light intensity drops to a minimum value when the coupling light turns off, showing a strong absorption. While at the moment of turning on the coupling light at a subsequent delayed time, the atomic medium shows a fast transient response. To account for the transient switching feature, in the time-dependent optical Bloch equation, we have to take the transverse relaxation dephasing process of atomic vapor into account, as well as the fluorescence relaxation along with the optical absorption. This work supplies a technique to quantify the transverse relaxation time scale and sensitively monitor its variation along the environment by observing the transient dynamics of coherent medium, which is helpful in characterizing the coherent feature of the atomic medium.

Sub-Hz Differential Rotational Spectroscopy of Enantiomers

We demonstrate for the first time high-precision differential microwave spectroscopy, achieving sub-Hz precision by coupling a cryogenic buffer gas cell with a tunable microwave Fabry–Perot cavity. We report statistically limited sub-Hz precision of (0.08 ± 0.72) Hz, observed between enantiopure samples of (R)-1,2-propanediol and (S)-1,2-propanediol at frequencies near 15 GHz. We confirm highly repeatable spectroscopic measurements compared to traditional pulsed-jet methods, opening up new capabilities in probing subtle molecular structural effects at the 10−10 level and providing a platform for exploring sources of systematic error in parity-violation searches. We discuss dominant systematic effects at this level and propose possible extensions of the technique for higher precision.

On the Feasibility of Rovibrational Laser Cooling of Radioactive RaF+ and RaH+ Cations

Polar radioactive molecules have been suggested to be exceptionally sensitive systems in the search for signatures of symmetry-violating effects in their structure. Radium monofluoride (RaF) possesses an especially attractive electronic structure for such searches, as the diagonality of its Franck-Condon matrix enables the implementation of direct laser cooling for precision experiments. To maximize the sensitivity of experiments with short-lived RaF isotopologues, the molecular beam needs to be cooled to the rovibrational ground state. Due to the high kinetic energies and internal temperature of extracted beams at radioactive ion beam (RIB) facilities, in-flight rovibrational cooling would be restricted by a limited interaction timescale. Instead, cooling techniques implemented on ions trapped within a radiofrequency quadrupole cooler-buncher can be highly efficient due to the much longer interaction times (up to seconds). In this work, the feasibility of rovibrationally cooling trapped RaF+ and RaH+ cations with repeated laser excitation is investigated. Due to the highly diagonal nature between the ionic ground state and states in the neutral system, any reduction of the internal temperature of the molecular ions would largely persist through charge-exchange without requiring the use of cryogenic buffer gas cooling. Quasirelativistic X2C and scalar-relativistic ECP calculations were performed to calculate the transition energies to excited electronic states and to study the nature of chemical bonding for both RaF+ and RaH+. The results indicate that optical manipulation of the rovibrational distribution of trapped RaF+ and RaH+ is unfeasible due to the high electronic transition energies, which lie beyond the capabilities of modern laser technology. However, more detailed calculations of the structure of RaH+ might reveal possible laser-cooling pathways.

sub-Hz Differential Rotational Spectroscopy of Enantiomers

Observation of parity-violating effects in chiral molecules is a long-standing challenge of the molecular spectroscopy community. In the microwave regime, the difference in transition frequencies between enantiomers is predicted to be below the mHz level, which is considerably beyond current experimental capabilities. The most promising future efforts combine vibrational spectroscopy, buffer gas cooling, and carefully chosen molecular candidates with large predicted parity-violating shifts. Here, we demonstrate for the first time high-precision differential microwave spectroscopy, achieving sub-Hz precision by coupling a cryogenic buffer gas cell with a tunable microwave Fabry-Perot cavity. We report statistically limited sub-Hz precision of (0.08±0.72) Hz, observed between enantiopure samples of (R)-1,2-propanediol and (S)-1,2-propanediol at frequencies near 15 GHz. We confirm highly repeatable spectroscopic measurements compared to traditional pulsed-jet methods, opening up new capabilities in probing subtle molecular structural effects at the 10−10 level and providing a platform for exploring sources of systematic error in parity-violation searches. We discuss dominant systematic effects at this level and propose possible extensions of the technique for higher precision.

Lead evaporation by VUV radiation of various spectral ranges

The results of an experimental study of the plasma formed by the evaporation of the lead target in the field of powerful broadband VUV radiation are presented. A pulse light-erosion magnetoplasma compressor (MPC’s) discharge is used as a model source of VUV radiation. “Gas filtration” of radiation is used to control the spectral composition – the discharge takes place in pure inert gases: in argon at 200 torr and neon at 400 torr. This allows us to manage the spectral distribution of radiation energy and to limit the energy of quants which irradiate the lead target with the first ionization potential of buffer gas. Shadow photography, toeplergrathy, double exposure laser holographic interferometry are used for diagnostics. Experimentally established different distribution of parameters in the lead plasma depending on the spectral composition of the impact radiation (the composition of buffer gas). It is shown that when the energy of quants increases (above the lead second ionization potential), a more even heating of the plasma layer is realized.