First-principles prediction and partial characterization of the vibrational states of water up to dissociation

A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron mass-velocity and Darwin corrections. For H₂¹⁶O, the PES has a dissociation energy of D₀ = 41 109 cm⁻¹ and supports 1150 vibrational energy levels up to 41 083 cm⁻¹. The deviation between the computed and the experimentally measured energy levels is below 15 cm⁻¹ for all the states with energies less than 39 000 cm⁻¹. Characterization of approximate vibrational quantum numbers is performed using several techniques: energy decomposition, wave function plots, normal mode distribution, expectation values of the squares of internal coordinates, and perturbing the bending part of the PES. Vibrational normal mode labels, though often not physically meaningful, have been assigned to all the states below 26 500 cm⁻¹ and to many more above it, including some highly excited stretching states all the way to dissociation. Issues to do with calculating vibrational band intensities for the higher-lying states are discussed.     

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.     

A fluorine-contained copolymer ultra-thin film: Stability and electrochemical corrosion behavior

A novel fluorine-contained random copolymer (2,3,4,5,6-pentafluorostyrene)-r-poly(4-vinyl benzocyclobutene) (P(PFSt-r-4-VBCB)) was synthesized, and then spin-coated onto Si substrates followed by thermal cross-linking to produce the copolymer ultra-thin films. Although the surface modification with the P(PFSt-r-4-VBCB) film was simple and did not rely on special surface chemical reactions, the film could decrease the surface energy significantly, more importantly; the film demonstrated excellent stability and corrosion resistance. This random copolymer film could find broad applications in modifying various solid surfaces to enhance the properties such as corrosion resistance and solvent resistance.     

Corrosion Products Formed on Mild Steel Samples Submerged in Various Aqueous Solutions

Corroded samples, from the steel shell of an industrial evaporator system were investigated. A protective magnetite layer had formed, which subsequently dissolved in localised areas, resulting in failure of the shell. To clarify the mechanisms involved, mild steel samples of similar composition to the steel shell were submerged in the condensate and experiments were performed at room temperature and at 90°C under both static and dynamic conditions for exposure times up to 30 days. Control samples were submerged in deionised water under similar conditions. The dynamic corrosion rates in the industrial condensate were a factor of 2 higher than the rates for the deionised water, whilst static corrosion rates, measured in both media, were lower by a factor of 3 to 4 found for the dynamic experiments. The corrosion products were identified by means of CEMS analyses. The main components were magnetite and oxyhydroxides of iron. Additional to the species mentioned, -Fe₂O₃, goethite and hematite formed.     

Fe–Mn–Al–C Alloys: a Study of Their Corrosion Behaviour in SO2 Environments

The corrosion reaction of four Fe–Mn–Al alloys exposed to a cycling, dry–humid, SO₂ (0.001% by volume) polluted atmosphere was studied. ICEMS, XPS, AES-SAM and transmission Mössbauer spectroscopy at different temperatures were employed to characterize the corrosion products. The analytical results indicate that (i) ferrihydrite is the main component of the rust; (ii) there is an abundant presence of Mn²⁺ and SO₃ ^2–/SO₄ ^2– on the top of the corrosion layer, the concentration of SO₄ ^2– increasing with the number of cycles; and (iii) the magnetic hyperfine pattern exhibited by the series of low-temperature spectra of the rust is quite different from that observed in the rust formed under similar corrosive environments on iron and weathering steel. This latter finding is correlated with a slow rate of transformation of the Fe³⁺ species formed at the early stages of corrosion into -FeOOH, the usual final product of this type of corrosion processes. The sulphate anions, abundant inside the electrolyte during the wet periods, could be incorporated to the ferrihydrite structure being responsible for the Mössbauer spectral pattern recorded from the corrosion products at low temperatures.     

大气中固体燃烧等离子体与微波相互作用的实验研究

 设计制造了含特定组分的化学药剂，利用热力学方法对其在大气中燃烧所产生的等离子体的电子密度进行了理论计算，对该等离子体对2~15 GHz波段微波的透射衰减和反射进行了测试。测试结果表明，该等离子体对该波段微波具有宽波段强吸收和弱反射性能，波段内的平均吸收大于25 dB，反射信号几乎淹没在背景噪声中。并从理论上分析了带电子与中性粒子的造成这一现象的主要原因是碰撞吸收。     

不同地区大气光学湍流内外尺度测量

 用光学湍流参数自动测量系统对内陆地区和沿海地区光学湍流内外尺度进行了大量的实验观测。分析了湍流尺度的日变化规律，给出了其频数分布。结果表明：两地内尺度的均值为十几mm，外尺度的均值约为2 m；内陆地区内尺度日变化趋势较为复杂，而外尺度的日变化趋势与湍流强度十分相似；沿海地区内外尺度与湍流强度均无明显关系。大气湍流尺度的大小和分布状态是随时间和空间变化的，因此，在估算实际大气湍流对光学系统的影响时，需要实测湍流尺度以便得到准确的结果。     

激光传输大气参量测量精度要求的数值分析

 就激光大气传输湍流热晕相互作用下大气参量测量误差对激光传输效果（平均功率密度）的影响进行了数值分析，并以典型的激光传输条件为例，分析了对激光大气传输影响最为敏感的3个大气参量——风速、吸收系数以及湍流结构常数的测量精度要求。综合不同传输距离下大气参量测量误差对传输效果的影响，大气风速的测量精度要求为±10%，吸收系数及湍流结构常数的测量精度要求分别为±5%和±15%。     

Evolution of spectroscopic information over the last decade and its effect on line-by-line calculations for validation of radiation codes for climate models

Five HITRAN's editions (since 1992) and three radically new H₂O spectral databases have been tested for their usefulness in line-by-line benchmark calculations for radiation code validations. The longwave calculations for the mid-latitude summer (MLS) atmosphere with the different HITRAN's editions revealed a good convergence (maximal discrepancies since decreased to in our flux calculations with 1992-2002 and 1996-2002 HITRAN's editions, respectively). The shortwave calculations with different HITRAN's editions revealed a good agreement: discrepancies in downward fluxes absorbed by the MLS atmosphere are less than , i.e. 0.5% for the all HITRAN's editions since 1992. It has been determined that it is unreasonable to replace HITRAN by any new H₂O spectral database in benchmark calculations, although they contain essentially more spectral lines than HITRAN (up to ∼10 times). Moreover, it has been found that no new database could be useful for explaining the “anomalous absorption” problem. Two latest water vapor continuum models have been tested as well. It has been found out that these models are the main source of uncertainties in the present and previous calculations: discrepancies for the MLS atmosphere reached ∼3 and in the longwave and shortwave flux calculations, respectively.     

Simultaneous determination of <Emphasis Type="SmallCaps">L</Emphasis>-arginine and its mono- and dimethylated metabolites in human plasma by high-performance liquid chromatography–mass spectrometry

A simple, fast, sensitive, and reproducible isocratic liquid chromatography–mass spectrometry (LC-MS) method coupled with an atmospheric pressure chemical ionization (APCI) interface for simultaneous separation and determination of L-arginine (ARG) and its methylated metabolites, N-monomethyl-L-arginine (MMA), N^G,N^G-dimethylarginine (asymmetric dimethyl arginine, ADMA), and N^G,N^G-dimethylarginine (symmetric dimethyl arginine, SDMA), in human plasma is presented. Sample pretreatment is not required other than deproteinization with 5-sulfosalicylic acid (5-SSA). Satisfactory chromatographic separation was achieved on a 2.0×150-mm Shimadzu VP-ODS column by using a mobile phase consisting of water/acetonitrile (90/10, v/v) containing 0.5% trifluoroacetic acid (TFA). Positive selective ion monitoring (SIM) mode was chosen for quantification of each analyte. The positively protonated molecular ions [M+H]⁺ of ARG, MMA, ADMA, and SDMA were monitored at m/z 175, 189, 203, and 203, respectively. L-Homoarginine was used as the internal standard (IS) for the assay. The limits of quantification (LOQs) were found to be 1.0 mol L^–1 for ARG, and 0.2 mol L^–1 for MMA, ADMA, and SDMA. The inter-assay precision and accuracy were in the range of 1.8–4.9% and –3.0–5.0%, respectively. The intra-assay precision and accuracy were in the order of 1.7–4.6 and –2.6–4.0%, respectively. The recoveries were between 90.0 and 106.6%. The levels of ARG, MMA, ADMA, and SDMA in human plasma were also determined using the developed method.