Measurements of long-term changes in atmospheric OCS (carbonyl sulfide) from infrared solar observations

Multi-decade atmospheric OCS (carbonyl sulfide) infrared measurements have been analyzed with the goal of quantifying long-term changes and evaluating the consistency of the infrared atmospheric OCS remote-sensing measurement record. Solar-viewing grating spectrometer measurements recorded in April 1951 at the Jungfraujoch station (46.5°N latitude, 8.0°E longitude, 3.58 km altitude) show evidence for absorption by lines of the strong ν₃ band of OCS at 2062 cm⁻¹. The observation predates the earliest previously reported OCS atmosphere remote-sensing measurement by two decades. More recent infrared ground-based measurements of OCS have been obtained primarily with high-resolution solar-viewing Fourier transform spectrometers (FTSs). Long-term trends derived from this record span more than two decades and show OCS columns that have remained constant or have decreased slightly with time since the Mt. Pinatubo eruption, though retrievals assuming different versions of public spectroscopic databases have been impacted by OCS ν₃ band line intensity differences of ∼10%. The lower stratospheric OCS trend has been inferred assuming spectroscopic parameters from the high-resolution transmission (HITRAN) 2004 database. Volume mixing ratio (VMR) profiles measured near 30°N latitude with high-resolution solar-viewing FTSs operating in the solar occultation mode over a 22 years time span were combined. Atmospheric Trace MOlecucle Spectroscopy (ATMOS) version 3 FTS measurements in 1985 and 1994 were used with Atmospheric Chemistry Experiment (ACE) measurements during 2004-2007. Trends were calculated by referencing the measured OCS VMRs to those of the long-lived constituent N₂O to account for variations in the dynamic history of the sampled airmasses. Means and 1-sigma standard deviations of VMRs (in ppbv, or 10⁻⁹ per unit air volume) averaged over 30-100 hPa from measurements at 25-35°N latitude are 0.334±0.089 ppbv from 1985 (ATMOS Spacelab 3 measurements), 0.297±0.094 ppbv from 1994 ATLAS 3 measurements, 0.326±0.074 ppbv from ACE 2004 measurements, 0.305±0.096 ppbv from ACE 2005 measurements, 0.328±0.074 from ACE 2006 measurements, and 0.305±0.090 ppbv from ACE measurements through August 2007. Assuming these parameters, we conclude that there has been no statistically significant trend in lower stratospheric OCS over the measurement time span. We discuss past measurement sets, quantify the impact of changes in infrared spectroscopic parameters on atmospheric retrievals and trend measurements, and discuss OCS spectroscopic uncertainties of the current ν₃ band parameters in public atmospheric databases.     

First measurements of the HCFC-142b trend from atmospheric chemistry experiment (ACE) solar occultation spectra

The first measurement of the HCFC-142b (CH₃CClF₂) trend near the tropopause has been derived from volume mixing ratio (VMR) measurements at northern and southern hemisphere mid-latitudes for the 2004–2008 time period from spaceborne solar occultation observations recorded at 0.02 cm⁻¹ resolution with the ACE (atmospheric chemistry experiment) Fourier transform spectrometer. The HCFC-142b molecule is currently the third most abundant HCFC (hydrochlorofluorocarbon) in the atmosphere and ACE measurements over this time span show a continuous rise in its volume mixing ratio. Monthly average measurements at northern and southern hemisphere mid-latitudes have similar increase rates that are consistent with surface trend measurements for a similar time span. A mean northern hemisphere profile for the time span shows a near constant VMR at 8–20 km altitude range, consistent on average for the same time span with in situ results. The nearly constant vertical VMR profile also agrees with model predictions of a long lifetime in the lower atmosphere.     

Trends in atmospheric halogen containing gases since 2004

The changes in the atmospheric concentration of 16 halogenated gases in the atmosphere have been determined using measurements made by the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS). ACE-FTS has been used to measure the change in concentration between 2004 and 2010 of CCl₄, CF₄, CCl₃F (CFC-11), CCl₂F₂ (CFC-12), C₂Cl₃F₃ (CFC-113), CH₃Cl, ClONO₂, COF₂, COCl₂, COClF, CHF₂Cl (HCFC-22), CH₃CCl₂F (HCFC-141b), CH₃CClF₂ (HCFC-142b), HCl, HF and SF₆ between 30°N and 30°S. ACE-FTS measurements were compared to surface measurements made by the AGAGE network and output from the SLIMCAT three-dimensional (3-D) chemical transport model, which is constrained by similar surface data. ACE-FTS measurements of CFCs show declining trends which agree with both AGAGE and SLIMCAT values. There are problems with the ACE-FTS retrievals of CFC-113 and HCFCs, with work currently ongoing to correct these problems. At lower altitudes the volume mixing ratio (VMR) of these species increase with altitude. This is due to problems with the retrievals at high beta angle (the angle between the orbital plane and the Earth-Sun vector). Although some of the retrievals have problems, we are confident that the trends are generally reliable. The concentrations of HCFCs appear to be increasing with ACE-FTS, SLIMCAT and AGAGE all showing positive trends. ACE-FTS measurements of the decomposition products (COFCl and COCl₂) do not show any significant trends. SLIMCAT data show a negative trend for COFCl which corresponds to the decrease in CFC-11, its assumed major source, during this time. COF₂ measurements from ACE-FTS show an increasing trend, while SLIMCAT shows a decreasing trend again linked to its assumed production from CFCs. ClONO₂ is highly photosensitive, thus the ACE-FTS occultations have been divided into local morning and evening occultations. Evening measurements of ClONO₂ show a decreasing trend in VMR, while morning measurements show an increasing trend. The reason for this difference is not understood at this time. The SLIMCAT output used in this study was not saved as local sunrise and sunset: therefore, only 24 h mean fields are available for ClONO₂. These SLIMCAT data show a decreasing trend. SLIMCAT and ACE-FTS both show an increasing trend in the VMR of HF and a decreasing trend in the VMR of HCl. These results illustrate the success of the Montreal Protocol in reducing ozone depleting substances. The reduction in anthropogenic chlorine emissions has led to a decrease in the VMR of stratospheric HCl. The replacement of CFCs with HCFCs has led to an increase in the VMR of HF in the stratosphere. As chlorine-containing compounds continue to be phased out and replaced by fluorine-containing molecules, it is likely that total atmospheric fluorine will continue increasing in the near future.     

Tropospheric emission spectrometer (TES) and atmospheric chemistry experiment (ACE) measurements of tropospheric chemistry in tropical southeast Asia during a moderate El Niño in 2006

High spectral resolution Fourier transform spectrometer (FTS) measurements of tropospheric carbon monoxide (CO) distributions show mixing ratios over Indonesia during October 2006 of ∼200 ppbv (10⁻⁹ per unit volume) in the middle troposphere. The elevated emissions were caused by intense and widespread Indonesian peat and forest fire emissions elevated compared to other years by the impact of a moderate El Niño/Soutern Oscillation (ENSO) event, which delayed that year's monsoon season and produced very dry conditions. Moderate resolution imaging spectrometer (MODIS) fire counts, atmospheric chemistry experiment (ACE) measurements of elevated mixing ratios of fire emission products and near infrared extinction, and back trajectory calculations for a sample measurement location near the time of maximum emissions provide additional evidence that the elevated 2006 emissions resulted primarily from the Indonesia fires. Lower CO mixing ratios measured by ACE and fewer MODIS fire counts in Indonesia during October 2005 indicate lower emissions than during 2006. Coincident profiles from the ACE agree within the uncertainties with those from the tropospheric emission spectrometer (TES) for pressure ranges and time periods with good TES sensitivity after accounting for its lower vertical sensitivity compared with the ACE FTS.     

Multi-decade measurements of the long-term trends of atmospheric species by high-spectral-resolution infrared solar absorption spectroscopy

Solar absorption spectra were recorded for the first time in 5 years with the McMath Fourier transform spectrometer at the US National Solar Observatory on Kitt Peak in southern Arizona, USA (31.91°N latitude, 111.61°W longitude, 2.09 km altitude). The solar absorption spectra cover 750-1300 and 1850-5000 cm⁻¹ and were recorded on 20 days during March-June 2009. The measurements mark the continuation of a long-term record of atmospheric chemical composition measurements that have been used to quantify seasonal cycles and long-term trends of both tropospheric and stratospheric species from observations that began in 1977. Fits to the measured spectra have been performed, and they indicate the spectra obtained since return to operational status are nearly free of channeling and the instrument line shape function is well reproduced taking into account the measurement parameters. We report updated time series measurements of total columns for six atmospheric species and their analysis for seasonal cycles and long-term trends. As an example, the time series fit shows a decrease in the annual increase rate in Montreal-Protocol-regulated chlorofluorocarbon CCl₂F₂ from 1.51±0.38% yr⁻¹ at the beginning of the time span to −1.54±1.28% yr⁻¹ at the end of the time span, 1 sigma, and hence provides evidence for the impact of those regulations on the trend.     

Detection of elevated tropospheric hydrogen peroxide (H2O2) mixing ratios in atmospheric chemistry experiment (ACE) subtropical infrared solar occultation spectra

We report measurements of hydrogen peroxide (H₂O₂) profiles from infrared solar occultation spectra recorded at 0.02 cm⁻¹ resolution by the atmospheric chemistry experiment (ACE) during 2004 and 2005. Mixing ratios as high as 1.7 ppbv (1 ppbv=1×10⁻⁹ per unit volume) were measured in the subtropical troposphere. Back trajectories, fire count statistics, and simultaneous measurements of other species from the same occultation provide evidence that the elevated H₂O₂ mixing ratios originated from a young biomass-burning plume. The ACE time series show only a few cases with elevated H₂O₂ mixing ratios likely because of the short lifetime of H₂O₂ and the limited sampling during biomass-burning time periods.     

The influence of temperature (20-1000 °C) on binary mixtures of solid solutions of CH3COOLi·2H2O-MgHPO4·3H2O

Thermally induced phase transitions (20-1000 °C) in the substrates and binary mixtures of CH₃COOLi·2H₂O(1)-MgHPO₄·3H₂O(11) have been analysed. Changes taking place on dehydration and thermal dissociation of binary mixtures prepared with percent molar ratios of 90-10% were studied by differential thermal analysis (TG, DTG, DTA), IR-spectroscopy and WAXS.The above-mentioned substrates changed their structure when heated for 1 h at 500 or 1000 °C. CH₃COOLi·2H₂O(1) (ID: 23-1171) changed the structure at 500 °C to that of Li₂CO₃ (ID: 22-1141), while at 1000 °C the structure was impossible to analyse as the compound reacted both with porcelain and with platinum (crucible materials). MgHPO₄·3H₂O(11) (Newberyite, ID: 35-780, 19-762) changed its structure at 500 °C to amorphous phase and at 1000 °C to Mg₂P₂O₇ (ID: 32-626).The following compounds were assayed in the respective binary mixtures heated at 500 °C for 1 h: 70% (1)-30%(11): LiMgPO₄ (ID: 18-735), MgO (ID: 4-829); 50%(1)-50%(11): LiMgPO₄ (ID: 18-735), Li₃PO₄ (ID: 25-1030); 30%(1)-70%(11): LiMgPO₄ (ID: 32-574); binary mixtures heated at 1000 °C contained the following compounds: 70%(1)-30%(11): LiMgPO₄ (ID: 32-574,18-735), Li₃PO₄ (ID: 15-760,25-1030), MgO (ID: 4-829); 50%(1)-50%(11): LiMgPO₄ (ID: 32-574, 18-735), MgO (ID: 4-829); 30%(1)-70%(11): LiMgPO₄ (ID: 18-735, 32-574), Mg₂P₂O₇ (ID: 22-1152, 8-38), Li₄SiO₄ (37-1472).     

Influence of crystallization on the spectral features of nano-sized ferroelectric barium strontium titanate (Ba0.7Sr0.3Tio3) thin films

Ferroelectric barium strontium titanate (Ba_0.7Sr_0.3TiO₃)(BST) thin films have been prepared from barium 2-ethylhexanoate [Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂]_, strontium 2-ethylhexanoate [Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂] and titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄ precursors using a modified sol-gel technique. The precursor except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on pre-cleaned quartz substrates by spin coating. The structural and optical properties of films annealed at different temperatures have been investigated. The as-fired films were found to be amorphous that crystallized to the tetragonal phase after annealing at 550 °C for 1 h in air. The lattice constants “a” and “c” were found to be 3.974 A and 3.990 A, respectively. The grain sizes of the films annealed at 450, 500 and 550 °C were found to be 30.8, 36.0 and 39.8 nm respectively. The amorphous film showed very high transparency (∼95%), which decreases slightly after crystallization (∼90%). The band gap and refractive index of the amorphous and crystalline films were estimated. The optical dispersion data are also analyzed in the light of the single oscillator model and are discussed.     

Etching reaction of methylchloride molecule on the GaAs (0 0 1)-2 × 4 surface

Adsorption process of methylchloride (CH₃Cl) on the GaAs (0 0 1)-2 × 4 surface was studied by a scanning tunnelling microscopy (STM) measurement. The arsenic rich 2 × 4 surface, which was prepared by molecular beam epitaxy (MBE), was exposed to a supersonic molecular beam of CH₃Cl with a kinetic energy of 0.06 eV. New bright spots appeared on the CH₃Cl exposed surface. They were largely observed at the “B-type” step edge and divided into two types according to their locations. It was suggested that new spots were due to weakly adsorbed CH₃Cl molecules without any dissociation. The adsorption mechanism of CH₃Cl molecule was also studied by an ab initio Hartree-Fock calculation, which explained the experimental results well.     

Preparation and textural characterisation of activated carbon from vine shoots (Vitis vinifera) by H3PO4—Chemical activation

An abundant and low-cost agricultural waste as vine shoots (Vitis vinifera) (VS), which is generated by the annual pruning of vineyards, has been used as raw material in the preparation of powder activated carbon (AC) by the method of chemical activation with phosphoric acid. After size reduction, VS were impregnated for 2 h with 60 wt.% H₃PO₄ solution at room temperature, 50 and 85 °C. The three impregnated products were carbonised at 400 °C. The product impregnated at 50 °C was heated either first at 150-250 °C and then at 400 °C or simply at 350-550 °C in N₂ atmosphere. The time of isothermal treatment after each dynamic heating was 2 h. The carbons were texturally characterised by gas adsorption (N₂, −196 °C), mercury porosimetry, and density measurements. FT-IR spectroscopy was also applied. Better developments of surface area and microporosity are obtained when the impregnation of VS with the H₃PO₄ solution is effected at 50 °C and for the products heated isothermally at 200 and 450 °C. The mesopore volume is also usually higher for the products impregnated and heated at intermediate temperatures.     

Chemical composition of ZrC thin films grown by pulsed laser deposition

ZrC films were grown on (1 0 0) Si substrates by the pulsed laser deposition (PLD) technique using a KrF excimer laser working at 40 Hz. The nominal substrate temperature during depositions was set at 300 °C and the cooling rate was 5 °C/min. X-ray diffraction investigations showed that films deposited under residual vacuum or under 2 × 10⁻³ Pa of CH₄ atmosphere were crystalline, exhibiting a (2 0 0)-axis texture, while those deposited under 2 × 10⁻² Pa of CH₄ atmosphere were found to be equiaxed and with smaller grain size. The surface elemental composition of as-deposited films, analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), showed the usual high oxygen contamination of carbides. Once the topmost 2-4 nm region was removed, the oxygen concentration rapidly decreased, down to around 3-8% only in bulk. Simulations of the X-ray reflectivity (XRR) curves indicated a smooth surface morphology, with roughness values below 1 nm (rms) and films density values of around 6.30-6.45 g/cm³, very close to the bulk density. The growth rate, estimated from thickness measurements by XRR was around 8.25 nm/min. Nanoindentation results showed for the best quality ZrC films a hardness of 27.6 GPa and a reduced modulus of 228 GPa.     

Effect of different dopant elements (Al,Mg and Ni) on microstructural,optical and electrochemical properties of ZnO thin films deposited by spray pyrolysis (SP)

In the present work we studied the influence of the dopant elements and concentration on the microstructural and electrochemical properties of ZnO thin films deposited by spray pyrolysis. Transparent conductive thin films of zinc oxide (ZnO) were prepared by the spray pyrolysis process using an aqueous solution of zinc acetate dehydrate [Zn(CH₃COO)₂·2H₂O] on soda glass substrate heated at 400 ± 5 °C. AlCl₃, MgCl₂ and NiCl₂ were used as dopant. The effect of doping percentage (2–4%) has been investigated. Afterwards the samples were thermally annealed in an ambient air during one hour at 500 °C. X-ray diffraction showed that films have a wurtzite structure with a preferential orientation along the (0 0 2) direction for doped ZnO. The lattice parameters a and c are estimated to be 3.24 and 5.20 ?, respectively. Transmission allowed to estimate the band gaps of ZnO layers. The electrochemical studies revealed that the corrosion resistance of the films depended on the concentration of dopants.     

The dehydrogenation of CH4 on Rh(1 1 1), Rh(1 1 0) and Rh(1 0 0) surfaces: A density functional theory study

CH₄ dehydrogenation on Rh(1 1 1), Rh(1 1 0) and Rh(1 0 0) surfaces has been investigated by using density functional theory (DFT) slab calculations. On the basis of energy analysis, the preferred adsorption sites of CH_x (x = 0-4) and H species on Rh(1 1 1), Rh(1 1 0) and Rh(1 0 0) surfaces are located, respectively. Then, the stable co-adsorption configurations of CH_x (x = 0-3) and H are obtained. Further, the kinetic results of CH₄ dehydrogenation show that on Rh(1 1 1) and Rh(1 0 0) surfaces, CH is the most abundant species for CH₄ dissociation; on Rh(1 1 0) surface, CH₂ is the most abundant species, our results suggest that Rh catalyst can resist the carbon deposition in the CH₄ dehydrogenation. Finally, results of thermodynamic and kinetic show that CH₄ dehydrogenation on Rh(1 0 0) surface is the most preferable reaction pathway in comparison with that on Rh(1 1 1) and Rh(1 1 0) surfaces.     

Thermal stability of alkoxy monolayers grafted on Si(1 1 1)

Direct grafting of organic monolayers on Si is of prime interest in order to give specific properties to a silicon surface. However, for microelectronics applications, this possibility is hampered by the limited stability of the grafted layers. It has been previously established that alkyl layers attached to Si surfaces through Si-C bonds become unstable at 250-300 °C, by desorption of alkenes. Changing the nature of the bonding to the surface might allow one to circumvent this desorption pathway and increase the layer stability. In our work, decanol and decyl aldehyde are reacted with the Si(1 1 1)-H surface at ∼100 °C during 20 h in order to obtain alkoxy monolayers. FTIR measurements performed in ATR geometry show that the grafted molecule surface coverage is on the order of 33% after reaction with decanol and 50% after reaction with decyl aldehyde. Characterization by AFM essentially reveals that the morphology of the grafted surfaces is unaffected as compared to that of Si-H surfaces. However, the edges of the terraces at alcohol-grafted surfaces exhibit some pitting, probably due to the presence of water in the grafting liquid. Thermal stability studies show that alkoxy chains progressively disappear from the Si surface between 200 and 400 °C. From the CH₂/CH₃ ratio in the CH region (2760-3070 cm⁻¹), it appears that the chains undergo progressive dissociation by C-C bond breaking before their complete disappearance from the surface. Therefore, the thermal behaviour of alkoxy monolayers appears quite distinct from that of alkyl monolayers that tend to leave the surface in a much narrower temperature range (250-350 °C), essentially via breaking of the Si-C bonds.     

The effects of Si3N4 interlayer on the thermal stability and hardness of Ti/TiNx (x = 0.5-1) nanolayered coatings

The polycrystalline Ti/TiN_x multilayer films were deposited by magnetron sputtering, and the as-deposited multilayer coatings were annealed at 500-800 °C for 2-4 h in vacuum. We investigated the effects of annealing temperature and annealing time on the microstructural, interfacial, and mechanical properties of the polycrystalline Ti/TiN_x multilayer films. It was found that the hardness increased with annealing temperature. This hardness enhancement was probably caused by the preferred crystalline orientation TiN(1 1 1). The X-ray reflectivity measurements showed that the layer structure of the coatings could be maintained after annealing at 500 °C and the addition of the Si₃N₄ interlayer to Ti/TiN_x multilayer could improve the thermal stability to 800 °C.     

A multispectrum analysis of the ν2 band of HCN: Part I. Intensities, broadening, and shift coefficients

Absolute intensities, self- and air-broadening coefficients, self- and air-induced shift coefficients and their temperature dependences have been determined for lines belonging to the P- and R-branches of the ν₂ band of H¹²C¹⁴N centered near 712 cm⁻¹. Infrared spectra of HCN in the 14-μm region were obtained at high resolution (0.002-0.008 cm⁻¹) using two different Fourier transform spectrometers (FTS), the McMath-Pierce FTS at the National Solar Observatory on Kitt Peak and the Bruker IFS 120HR FTS at the Pacific Northwest National Laboratory. Spectra were recorded with 99.8% pure HCN as well as lean mixtures of HCN in air at various temperatures ranging between +26 and −60 °C. A multispectrum nonlinear least squares technique was used to fit selected intervals of 36 spectra simultaneously to obtain the line positions, intensities, broadening, and shift parameters. The measured line intensities were analyzed to determine the vibrational band intensity and the Herman-Wallis coefficients. The measured self-broadening coefficients vary between 0.2 and 1.2 cm⁻¹ atm⁻¹ at 296 K, and the air-broadening coefficients range from 0.08 to 0.14 cm⁻¹ atm⁻¹ at 296 K. The temperature dependence exponents of self-broadening range from 1.46 to −0.12 while the corresponding exponents for air broadening vary between 0.58 and 0.86. The present measurements are the first known determination of negative values for the temperature dependence exponents of HCN-broadening coefficients. We were able to support our self-broadening measurements with appropriate theoretical calculations. Our present measurements are compared, where possible, with previous measurements for this and other HCN bands, as well as the parameters that are included in the 2000 and 2004 editions of the high-resolution transmission (HITRAN) database.     

Synthesis process and the luminescence properties of rare earth doped NaLa(WO4)2 nanoparticles

Rare earth doped NaLa(WO₄)₂ nanoparticles have been prepared by a simply hydrothermal synthesis procedure. The X-ray diffraction (XRD) pattern shows that the Eu³⁺-doped NaLa(WO₄)₂ nanoparticles with an average size of 10-30 nm can be obtained via hydrothermal treatment for different time at 180 °C. The luminescence intensity of Eu³⁺-doped NaLa(WO₄)₂ nanoparticles depended on the size of the nanoparticles. The bright upconversion luminescence of the 2 mol% Er³⁺ and 20 mol% Yb³⁺ codoped NaLa(WO₄)₂ nanoparticles under 980 nm excitation could also be observed. The Yb³⁺-Er³⁺ codoped NaLa(WO₄)₂ nanoparticles prepared by the hydrothermal treatment at 180 °C and then heated at 600 °C shows a 20 times stronger upconversion luminescence than those prepared by hydrothermal treatment at 180 °C or by hydrothermal treatment at 180 °C and then heated at 400 °C.     

A new quasi-one-dimensional molecular solid based on Ni(mnt)2 anion: Crystal structure and spin-gap transition

A new molecular solid, [1-(4′-bromo-2′-fluorobenzyl)-4-dimetylaminopyridinium]-bis(maleonitriledithiolato)nickel(III), (BrFBzPyN(CH₃)₂(Ni(mnt)₂)(1), has been prepared and characterized by elemental analyses, IR, ESI-MS spectra, single crystal X-ray diffraction and magnetic measurements. Compound 1 crystallizes in the orthorhombic space group Pnma, a=20.579(4) Å, b=7.078(1) Å, c=17.942(4) Å, α=β=γ=90°, V=2613.3(9) Å³, Z=4. The Ni(III) ions of 1 form a quasi-one-dimensional Zigzag magnetic chain within a Ni(mnt)₂⁻ column through Ni?S, S?S, Ni?Ni, or π?π interactions with an Ni?Ni distance of 4.227 Å. Magnetic susceptibility measurements in the temperature range 2-300 K show that 1 exhibits a spin-gap transition around 200 K, and antiferromagnetic interaction in the high-temperature phase (HT) and spin gap in the low-temperature phase (LT). The transition for 1 is second-order phase transition as determined by DSC analyses.     

Submillimeter spectrum of methyl bromide (CH3Br)

Methyl bromide is a ubiquitous component of the atmosphere, but has yet to be remotely detected in the upper atmosphere. Due to the strong ozone depletion capability of the activated bromine species, the total atmospheric bromine load needs to be carefully monitored. Combined analysis of precise measurements and cataloging of the rotational spectrum of methyl bromide may enable its concentration to be monitored with future remote sensing instrumentation. In an effort to extend and improve previous work for this molecule, the spectrum of CH₃Br has been measured at JPL. Using an isotopically enriched ¹³CH₃Br (90%) sample, spectra have been recorded from 750 to 1200 GHz. Quantum number assignments cover the CH₃⁷⁹Br, CH₃⁸¹Br, ¹³CH₃⁷⁹Br and ¹³CH₃⁸¹Br isotopologues with J < 66 and K < 17 for the ground and ν₃ vibrational states. The dataset for the ¹²C isotopologues is more precise than previous THz measurements resulting in reductions of rotational and distortion parameter uncertainties by factors of 2-15. Parameters of the ν₃ state of the ¹²C isotopologues are improved by 2-105. The spectra of the ¹³C isotopologues are the first reported beyond J = 2.     

Atomic and molecular adsorption on Pt(1 1 1)

The adsorption of several atomic (H, O, N, S, and C) and molecular (N₂, HCN, CO, NO, and NH₃) species and molecular fragments (CN, CNH₂, NH_2, NH, CH₃, CH₂, CH, HNO, NOH, and OH) on the (1 1 1) facet of platinum, an important industrial and fuel cell catalyst, was studied using self-consistent periodic density functional theory (DFT-GGA) calculations at a coverage of 1/4 ML. The best binding site, energy, and position, as well as an estimated diffusion barrier, of each species were determined. The binding strength for all the species can be ordered as follows: N₂ < NH₃ < HCN < NO < CO < CH₃ < OH < NH₂ < H < CN < NH < O < HNO < CH₂ < NOH < CNH₂ < N < S < CH < C. Although the atomic species generally preferred fcc sites, there was no clear trend in site preference by the molecular species or molecular fragments. The vibrational frequencies of all the stable adsorbates in their best and second best adsorption sites were calculated and found to be in good agreement with experimental values reported in the literature. Finally, the decomposition thermochemistry of NOH, HNO, NO, NH₃, N₂, CO, and CH₃ was analyzed.