Photoionization mass spectrometry - A mating of vacuum UV optics and mass spectrometry
Photoionization mass spectrometry, considering application to appearance potentials determination, ion-neutral reactions and gas analysis
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Photoionization mass spectrometry, considering application to appearance potentials determination, ion-neutral reactions and gas analysis
Developments in bulk crystal growth research for electro-optical devices in the Center for Photonic Materials and Devices since its establishment have been reviewed. Purification processes and single crystal growth systems employing physical vapor transport and Bridgman methods were assembled and used to produce high purity and superior quality wide bandgap materials such as heavy metal halides and II-VI compound semiconductors. Comprehensive material characterization techniques have been employed to reveal the optical, electrical and thermodynamic properties of crystals, and the results were used to establish improved material processing procedures. Postgrowth treatments such as passivation, oxidation, chemical etching and metal contacting during the X-ray and gamma-ray device fabrication process have also been investigated and low noise threshold with improved energy resolution has been achieved.
Transmissive scanning elements for coherent laser radar systems are typically optical wedges, or prisms, which deflect the lidar beam at a specified angle and are then rotated about the instrument optical axis to produce a scan pattern. The wedge is placed in the lidar optical system subsequent to a beam-expanding telescope, implying that it has the largest diameter of any element in the system. The combination of the wedge diameter and asymmetric profile result in the element having very large mass and, consequently, relatively large power consumption required for scanning. These two parameters, mass and power consumption, are among the instrument requirements which need to be minimized when designing a lidar for a space-borne platform. Reducing the scanner contributions in these areas will have a significant effect on the overall instrument specifications, Replacing the optical wedge with a diffraction grating on the surface of a thin substrate is a straight forward approach with potential to reduce the mass of the scanning element significantly. For example, the optical wedge that will be used for the SPAce Readiness Coherent Lidar Experiment (SPARCLE) is approximately 25 cm in diameter and is made from silicon with a wedge angle designed for 30 degree deflection of a beam operating at approx. 2 micrometer wavelength. The mass of this element could be reduced by a factor of four by instead using a fused silica substrate, 1 cm thick, with a grating fabricated on one of the surfaces. For a grating to deflect a beam with a 2 micrometer wavelength by 30 degrees, a period of approximately 4 micrometers is required. This is small enough that fabrication of appropriate high efficiency blazed or multi-phase level diffractive optical gratings is prohibitively difficult. Moreover, bulk or stratified volume holographic approaches appear impractical due to materials limitations at 2 micrometers and the need to maintain adequate wavefront quality. In order to avoid the difficulties encountered in these approaches, we have developed a new type of high-efficiency grating which we call a Stratified Volume Diffractive Optical Element (SVDOE). The features of the gratings in this approach can be easily fabricated using standard photolithography and etching techniques and the materials used in the grating can be chosen specifically for a given application, In this paper we will briefly discuss the SVDOE technique and will present an example design of a lidar scanner using this approach. We will also discuss performance predictions for the example design.
This paper outlines cryogenic Y-joint testing at Langley Research Center (LaRC) to validate the performance of optical fiber Bragg grating strain sensors for measuring strain at liquid helium temperature (-240 C). This testing also verified survivability of fiber sensors after experiencing 10 thermal cool-down, warm-up cycles and 400 limit load cycles. Graphite composite skins bonded to a honeycomb substrate in a sandwich configuration comprised the Y-joint specimens. To enable SHM of composite cryotanks for consideration to future spacecraft, a light-weight, durable monitoring technology is needed. The fiber optic distributed Bragg grating strain sensing system developed at LaRC is a viable substitute for conventional strain gauges which are not practical for SHM. This distributed sensing technology uses an Optical Frequency Domain Reflectometer (OFDR). This measurement approach has the advantage that it can measure hundreds of Bragg grating sensors per fiber and the sensors are all written at one frequency, greatly simplifying fiber manufacturing. Fiber optic strain measurements compared well to conventional strain gauge measurements obtained during these tests. These results demonstrated a high potential for a successful implementation of a SHM system incorporating LaRC's fiber optic sensing system on the composite cryotank and other future cryogenic applications.
Miniature optical gas sensors based on luminescent materials have shown great potential as alternatives to NIR-based gas sensor systems for the Portable Life Support System (PLSS). The unique capability of luminescent sensors for carbon dioxide and oxygen monitoring under wet conditions has been reported, as has the fast recovery of humidity sensors after long periods of being wet. Lower volume and power requirements are also potential advantages over both traditional and advanced non-dispersive infrared (NDIR) gas sensors, which have so far shown longer life than luminescent sensors. In this paper we present the most recent results in the development and analytical validation of a compact multi-gas sensor unit based on luminescent sensors for the PLSS. Results of extensive testing are presented, including studies conducted in Intelligent Optical Systems laboratories, a United Technologies Corporation Aerospace Systems (UTC) laboratory, and a Johnson Space Center laboratory. The potential of this sensor technology for gas monitoring in PLSSs and other life support systems, and the advantages and limitations found through detailed sensor validation are discussed.
When cloud properties are retrieved from satellite observations, the calculations apply 1D theory to the 3D world: they only consider vertical structures and ignore horizontal cloud variability. This presentation discusses how big the resulting errors can be in the operational retrievals of cloud optical thickness. A new technique was developed to estimate the magnitude of potential errors by analyzing the spatial patterns of visible and infrared images. The proposed technique was used to set error bars for optical depths retrieved from new MODIS measurements. Initial results indicate that the 1 km resolution retrievals are subject to abundant uncertainties. Averaging over 50 by 50 km areas reduces the errors, but does not remove them completely; even in the relatively simple case of high sun (30 degree zenith angle), about a fifth of the examined areas had biases larger than ten percent. As expected, errors increase substantially for more oblique illumination.
Introduction:Orbiter data indicatethe presence of carbonates in severallocations on the surface of Mars[1],but Jezero crater, landing site of the Perseverancerover,is the only known location where carbonatesap-pear coincident with evidence of fluvialand lacustrineactivity [2].On Earth, carbonates in close proximity to these paleoenvironments mayindicatethe presence of past microbial life,like stromatolites[3], that could re-sult inbiosignatures [2]. However,in other cases,car-bonates can also form throughthe alteration of mafic materialwiththe introductionof carbonic acid[4].Hy-drated magnesites have also been found in evaporative environments along lake shores, and in playas[5,6,7].Correctly interpreting past carbonates on Mars is there-fore critical in the search for past signs of life. In Jezero crater,both thenorthernand western fans haveMg-rich carbonates intermixed with olivine-rich material[8].According to CRISM data, magnesite(MgCO3), along with hydromagnesite(Mg5(CO3)4(OH)2•4H2O), arepotential candidatesfor these Mg-carbonates [2]. Considering the spatial con-text with olivine,there aremultiplepotential explana-tions for the presence ofMg-carbonatesin this locationincludingin-situformation via alterationof olivine-rich materialwith carbonic acid,transportationfrom farther up in the watershed, or precipitation of lacustrine car-bonates[2]. The formation of hydromagnesite rather than magnesite is favored when Mg2+saturated solutions have a high CO32-/HCO3-ratio, which, on Earth, is thought to be caused byinflow of groundwater [4]. Additionally, Mg-carbonates tend to precipitate under high pH condi-tions and are unstable at lower pH conditions [5]. Hy-dromagnesite is stable at atmospheric CO2pressure and temperature conditions common to most Earth surface environments [9]. However, it is subject to transfor-mation to magnesite after dehydration and concomitant brucite formation or dissolution and reprecipitation [10].Previousresearch suggests that hydrated car-bonates, including hydromagnesite, can formas weath-ering productsof mafic minerals in the presenceof H2O and CO2in subfreezing temperatures and would not de-hydrate under Martian atmospheric conditions [11,12].It is critical to understand the formation conditions of Mg-carbonatesbecause of the different implications for the past history of Martian environments. Therefore, in this work we are investigating the weathering of Mg-carbonatesin arid environments to helpbetter understand Mg-carbonates in Jezero crater. Study Area:The Ala-Mar Mines(East and West)near Ely, NVare the site ofmultiple magnesitedepositsfound within a calcareous tuff formationthat overlies Tertiary aged volcanic rocks.Here,magnesiteis formed via the alteration of the calcareous tuff and occurs innodules, veins,and lenses[13]. Previous work suggests magnesite deposits are associated with faults [13]. Within the West Mine, magnesite can be found in two maincontexts: (1) relatively circular zones of cauli-flower-like material found within (2) a more massivelensthat is heavily fractured on the surface.Methods.Samplesof both the cauliflower texture and more massive materialwere collectedat Ala Mar West Mine. Both samples were thenpowdered, sieved and analyzed with an inXitu Terra Portable XRD. The program QualX was used to identify potential mineral phases [14].Both samples were also optically inspected using 10x and 20x hand lenses.Figure 1. XRD patterns for the cauliflower magnesite (top) and massive magnesite (bottom). Ongoing and future work on the samples discussed above includes scanning electron microscopy (SEM), electron microprobe analysis (EMPA), and near-infra-red spectroscopy to determine whether hydromagnesite is present. Separation and analysis of the clay-size frac-tionby XRD will helpto better identify any phyllosili-cate phases present. Results and Discussion:Both textures are a white to light tan with a porcelain luster on weathered sur-faces, along with minor iron staining in some areas. Likewise, both textures are white with a porcelain luster on fresh surfaces. When broken apart, the massive mag-nesite shows macroscopic crystals, unlike the cauli-flower magnesite. XRD analysis shows that both samples have high concentrationsof magnesite with lesser amounts of thecarbonatemineral huntite(Mg3Ca(CO3)4; Figure1).The more massive samplecontainsa serpentine-groupmineral,with lizardite being apotential candidate. The cauliflower sample has several minor peaks that may correspond to hydromagnesite(Figure 1), although more work is needed to confirm this.Additionally, thecauliflower deposits closely resemble hydromagnesite deposits found in southwestern Turkey, formed via mi-crobialites[15].As such, it is likely that moreaqueous alterationor weatheringis occurring at the locations where the cauliflower magnesite is present. However, additional field work will need to be conducted to con-firm this hypothesis. Conclusions and Future Work:Future work will include field mapping of fault locations andadditional samplingof the different magnesite types as well as of the calcareous tuffmaterial.We will also look specifi-cally for potential weathering products of magnesite in this arid location, which may yield important insight into the Mg-carbonates located in Jezero crater. XRD analyses on aPANalytical XRDusing non-ambient stages will be used to investigate the stability of hydro-magnesiteat different humiditiesand temperatures, which has implications for samples to bereturned to Earth in the future. Additionally, thermal and evolved gas analysis of magnesite and hydromagnesite will be compared to results from Gale Craterto help interpret the mineralogy inthat location[16]. The results of this research will further ourunderstanding of carbonate for-mationin volcanic settingsandtheirweathering pro-cessesin arid environments. Acknowledgments:We acknowledge funding for this research from Jacobs Technology at the Johnson Space Center.We would also like to thank Ngoc Luu, Christopher Adcock, Richard Allanson, and the rest of the UNLV Soil Science Teamfor their continued sup-portwith troubleshooting and otherlab work. References:[1] Ehlmann, B.L., and Edwards, C.S. (2014) Annual Review of Earth and Planetary Sci., 42, 291–315. [2] Horgan, B.H.N., et al. (2020) Icarus, 339, 113526. [3] Bosak, T., et al. (2013) Annual Review of Earth and Planetary Sci, 41, 21–44. [4] Pohl, W.L. (1989) Gebriider Borntraege, 28, 1-13. [5] Müller, G., et al. (1972) Die Naturwissenschaften, 59, 158–164. [6] Walter, M.R., et al. (1973) Journal of Sedimentary Pe-trology, 43, 1021–1030. [7] Braithwaite, C.J.R., and Zedef, V. (1994) Sedimentary Geology, 92, 1–5. [8] Goudge, T.A., et al. (2015) JGR: Planets, 120, 775–808. [9] Langmuir, D. (1965) Journal of Geology, 73, 730–754. [10] Zhang, P., et al. (2000) Applied Geo-chem., 286, 1748–1753. [11] Calvin, W.M., et al. (1994) JGR, 99, 14659-14675. [12]Russell, M.J., et al. (1999) Journal of the Geological Society of London, v. 156, p. 869–888. [13] Faust, G.T., and Callaghan, E. (1948) GSA Bulletin, 59, 11–74. [14] Altomare, A., et al. (2015) J. of Applied Crystallography, 48, 598–603. [15] Zedef, V.,et al. (2000) Economic Geology, 95, 429–445. [16] Leshin, L.A. et al., (2013) Science, 341, 1–9
Thin cirrus clouds (with optical depth tau much less than 1) play a potentially important role in the Earth atmosphere. The Moderate Resolution Imaging Spectroradiometer (MODIS) onboard the Terra satellite has a channel at 1.375 microns that is specifically designed to detect these clouds. During two three-day periods from December 2000 and June 2001, I show that thin cirrus clouds are ubiquitous throughout the tropics. These thin cirrus generally have optical depths below 0.05 and appear with greater frequency and optical depth near deep convection. Regressing top-of-atmosphere outgoing longwave flux data from the Clouds and the Earth's Radiant Energy System (CERES) against optical depth, we calculate that these thin clouds decrease outgoing longwave flux by approx. 1 W/sq m/(0.01 tau). This translates into longwave forcing of several W/sq m near convection and zero away from convection. Averaging over the whole tropics, these thin cirrus decrease average longwave forcing is approx. 1.4 W/sq m.
A solid state model for quantum computation has potential advantages in terms of the ease of fabrication, characterization, and integration. The fundamental requirements for a quantum computer involve the realization of basic processing units (qubits), and a scheme for controlled switching and coupling among the qubits, which enables one to perform controlled operations on qubits. We propose a model for quantum computation based on optically coupled quantum dot arrays, which is computationally similar to the atomic model proposed by Cirac and Zoller. In this model, individual qubits are comprised of two coupled quantum dots, and an array of these basic units is placed in an optical cavity. Switching among the states of the individual units is done by controlled laser pulses via near field interaction using the NSOM technology. Controlled rotations involving two or more qubits are performed via common cavity mode photon. We have calculated critical times, including the spontaneous emission and switching times, and show that they are comparable to the best times projected for other proposed models of quantum computation. We have also shown the feasibility of accessing individual quantum dots using the NSOM technology by calculating the photon density at the tip, and estimating the power necessary to perform the basic controlled operations. We are currently in the process of estimating the decoherence times for this system; however, we have formulated initial arguments which seem to indicate that the decoherence times will be comparable, if not longer, than many other proposed models.
Two optical-beam-forming concepts selected for development of phased-array antennas. Involve use of novel combinations of optical and electronic techniques to distribute radio-frequency signal to or from antenna elements in array: phase and amplitude of radio-frequency signal traveling to or from each element controlled in such way to cause array as whole to transmit or receive signal in desired spatial pattern, steered, narrowed, broadened, or otherwise varied. Techniques result in compact, lightweight beam-steering antennas. Potential applications include steered-beam or quasi-optical microwave antennas in communication and radar systems, remote control of antennas in general, and photonic communication. With some modifications, transmitting and receiving configurations incorporated into single system.
A significant problem facing the optical satellite calibration community is limited knowledge of the uncertainties associated with fundamental measurements, such as surface reflectance, used to derive satellite radiometric calibration estimates. In addition, it is difficult to compare the capabilities of calibration teams around the globe, which leads to differences in the estimated calibration of optical satellite sensors. This paper reports on two recent field campaigns that were designed to isolate common uncertainties within and across calibration groups, particularly with respect to ground-based surface reflectance measurements. Initial results from these efforts suggest the uncertainties can be as low as 1.5% to 2.5%. In addition, methods for improving the cross-comparison of calibration teams are suggested that can potentially reduce the differences in the calibration estimates of optical satellite sensors.
The desire to transmit high frequency, microwave RF signals over fiber optic cables has necessitated the need for electro-optic modulation devices. However, in order to reap these potential benefits, it is necessary to develop the devices and their associated fabrication processes, particularly those processes associated with the poling of the devices. To this end, we entered into a cooperative research agreement with Richard Kunath of NASA LeRC. A graduate student in my group, Tony Kowalczyk, worked closely with the group at NASA to develop processes for construction of a microwave frequency electro-optic modulator. Materials were commercially obtained from Amoco Chemical and in collaboration with Lockheed-Martin. The photolithography processes were developed at NASA LeRC and the electric-field poling process was carried out in our laboratory at CWRU. During the grant period, the poling process conditions were investigated for these multilayer devices. Samples were poled and the resulting nonlinear optical properties were evaluated in our laboratory. Following the grant period, Kowalczyk went to NASA under a NRC fellowship, and I continued to collaborate as a consultant. Publications listed at the end of this report came out of this work. Another manuscript is in preparation and will be submitted shortly.
Information on the field and particle interfaces of electron bombardment ion thruster systems was summarized. Major areas discussed were the nonpropellant particles, neutral propellant, ion beam, low energy plasma, and fields. Spacecraft functions and subsystems reviewed were solar arrays, thermal control systems, optical sensors, communications, science, structures and materials, and potential control.
This paper collates and summarizes information on the field and particle interfaces of electron bombardment ion thruster systems. Major areas discussed are the nonpropellant particles, neutral propellant, ion beam, low energy plasma, and fields. Spacecraft functions and subsystems reviewed are solar arrays, thermal control systems, optical sensors, communications, science, structures and materials, and potential control. An appendix is included to facilitate identification of specific interaction areas.
It is shown that a transform-pair relationship exists between incident and scattered fields from an infinite, perfectly conducting reflector of arbitrary shape, when the physical optics approximation is applied. As an example of potential applications, this relationship is used to synthesize a reflector feed pattern required to produce a desired far-field pattern from a given paraboloidal reflector.
A few state-of-the-art optical image processing techniques are described and their potential applications to the ACPL experiments are suggested. The discussion also includes the selection of recording media in the present system and the enhancement of signal-to-noise ratio for the expected data from ACPL.
Ion traps are exciting candidates as future precision frequency sources. Recent developments demonstrate that mercury ion frequency standards are capable of a stability performance comparable to commercial cesium standards. There is, however, considerable room for improvement with regard to the signal to noise problem. The 40 GHz microwave frequency implies that a careful design should be implemented to ensure the elimination of the unwanted side bands in the microwave pump signal. A long life, high performance light source to be used in a trapped mercury ion microwave standard must be developed and the long term performance of a trapped mercury ion microwave standard must be investigated. While newly proposed two photon pumping schemes in conjuction with mercury ions promise exciting developments for both microwave and optical frequency standards, other ions that may be potential candidates should be evaluated for their usefulness.
A potential model is presented for the origin of optical activity in polypeptides on the primitive earth due to enantiomeric enrichment in succeeding polymerization-hydrolysis cycles. The model was developed in experiments with the polymerization of a DL-leucine N-carboxyanhydride mixture with a 31.2% enantiomeric excess of the L isomer with sodium methoxide initiator to yield a polyleucine product which was in turn partially hydrolyzed by acid. The polymerization-hydrolysis was found to produce a net 23.8% increase in the enantiomeric excess of the remaining unhydrolyzed polypeptide (14.2% from the polymerization and 9.6% from the partial hydrolysis). On the basis of these results, it is suggested that a slight excess produced by an appropriate chiral physical process may be enhanced by cycles of stereoselective polymerization and hydrolysis driven by fluctuating wet and dry environmental cycles on the primitive earth.