Optimization of magnetic field sweep and field modulation amplitude for continuous-wave EPR oximetry

For continuous-wave electron paramagnetic resonance spectroscopy, what settings of magnetic field sweep width and field modulation amplitude yield the best accuracy in estimated linewidth? Statistical bounds on estimation error presented in this work provide practical guidance: set the sweep width and modulation amplitude to 8 and 4 times the half-width half-maximum linewidth, Γ, respectively. For unknown linewidths in the range [Γ(min),Γ(max)] the worst-case estimation error is minimized by using settings designed for Γ(max). The analysis assumes a Lorentzian lineshape and a constant modulation amplitude across the extent of the irradiated paramagnetic probe. The analytical guidelines are validated using L-band spectroscopy with a particulate LiNc-BuO probe.     

Adsorbate motions induced by vibrational mode coupling

Adsorbate motions are discussed with a primary attention focused on the coupling between a vibrational mode excited by ultrafast laser heated hot-electrons or by inelastic tunneling electrons with scanning tunneling microscope and the reaction coordinate (RC) mode. Recent experimental results have demonstrated an efficient reaction pathways involving an indirect excitation of a frustrated translational mode, rather than its direct excitation for adsorbate hopping on surfaces. Elementary processes are briefly described for hopping of CO molecules on a laser heated stepped Pt surface, where excitation of the frustrated rotation mode has been found to plays an indispensable. Calculation of the inelastic tunneling current (ITC) for excitation of the C-O stretch mode of a CO molecule is combined with a theory of anharmonic mode coupling to activate the frustrated translation mode above the barrier. The hopping rate as a function of the bias voltage agrees with the experimental result. An unified theory of single-, and two-electron processes for ITC-induced motions induced by an indirect excitation of the RC-mode via mode coupling is also applied to reproduce a crossover from hopping to desorption of a single NH₃ molecule on Cu(1 0 0) with an increase in the tunneling current.     

CO2-broadened water in the pure rotation and ν2 fundamental regions

The CO₂-broadened water coefficients (half-widths, line shifts, and temperature dependence of the widths) are predicted using a fully complex Robert-Bonamy formulation for the 937 allowed and forbidden perpendicular type transitions of (000)-(000) between 200 and 900 cm⁻¹ in order to facilitate atmospheric remote sensing of Mars and Venus. In addition, empirical Lorentz line widths and pressure-induced frequency-shifts of CO₂-broadened H₂¹⁶O are obtained at room temperature for 257 perpendicular transitions of the (010)-(000) fundamental. For this, calibrated spectra recorded at 0.0054 cm⁻¹ resolution are measured assuming Voigt line shapes. For transitions between 1287 and 1988 cm⁻¹ with rotational quanta up to J = 13 and K_a = 6, the widths vary from 0.045 to 0.212 cm⁻¹ atm⁻¹ at 300 K; the pressure-shifts are quite large and range from −0.0386 to +0.0436 cm⁻¹ atm⁻¹. For the (010)-(000) band, the RMS and mean observed and calculated differences for CO₂-broadened H₂O half-widths are 12% and −1.9%, respectively, while the RMS and mean ratios of the observed and calculated pressure-induced shift coefficients are 1.6 and 0.79, respectively. For pairs of transitions involving K_a = 0 and 1, such as 2_0 2 ← 3_1 3 and 3_1 3 ← 2_0 2, both the calculated and observed pressure induced shifts in positions are opposite in sign and often similar in magnitude. The data are too limited to characterize vibrational dependencies of the widths, however.     

液相基质中重金属元素激光诱导击穿光谱实验参数的优化

针对混合溶液中重金属元素的激光诱导击穿光谱(LIBS)测量系统,为提高测量系统的检测灵敏度,以提高混合溶液中Ca和Cr金属元素LIBS光谱线强度的信噪比为目标,对LIBS测量系统中的激光脉冲能量、液相样品流速、ICCD门宽、延时等实验参数进行了优化,得到最优化参数激光脉冲能量、样品流速、ICCD门宽、延时分别为35 m J、30 ml/min、1400 ns和2400 ns,为降低LIBS技术应用于混合溶液中痕量重金属元素的检出限提供了实验参数支撑.     

浅析波谱分析课程教学改革

根据在波谱分析课程教学中遇到的一些实际问题,本文探讨了便于波谱分析课程教学的几种方法,并收到了较好的教学效果.     

High-resolution infrared and theoretical study of four fundamental bands of gaseous 1,3,4-oxadiazole between 800 and 1600 cm

The Fourier transform infrared spectrum of gaseous 1,3,4-oxadiazole, C₂H₂N₂O, has been recorded in the 800–1600 cm⁻¹ wavenumber region with a resolution around 0.0030 cm⁻¹. The four fundamental bands ν₉(B₁; 852.5 cm⁻¹), ν₁₄(B₂; 1078.5 cm⁻¹), ν₄(A₁; 1092.6 cm⁻¹), and ν₂(A₁; 1534.9 cm⁻¹) are analyzed by the standard Watson model. Ground state rotational and quartic centrifugal distortion constants are obtained from a simultaneous fit of ground state combination differences from three of these bands and previous microwave transitions. Upper state spectroscopic constants are obtained for all four bands from single band fits using the Watson model. The ν₄ and ν₁₄ bands form a c-Coriolis interacting dyad, and the two bands are analyzed simultaneously by a model including first and second order Coriolis resonance using the ab initio predicted Coriolis coupling constant . An extended local resonance in ν₂ is explained as higher order b-Coriolis type resonance with ν₆ + ν₁₀, which is further perturbed globally by the ν₁₅ + ν₁₀ level. A fit of selected low-J transitions to a triad model including ν₂(A₁), ν₆ + ν₁₀(B₁), and ν₁₅ + ν₁₀(A₂) using an ab initio calculated Coriolis coupling constant is performed.The rotational constants, ground state quartic centrifugal distortion constants, anharmonic frequencies, and vibration–rotational constants (α-constants) predicted by quantum chemical calculations using a cc-pVTZ and TZ2P basis with B3LYP methodology, are compared with the present experimental data, where there is generally good agreement. A complete set of anharmonic frequencies and α-constants for all fundamental levels of the molecule is given.     

Determination of line strengths for selected transitions in the v2 band relative to the v1 and v5 bands of H2CO

The spectral line strengths in the v₂ band of H₂CO (segments spanning 1720-) have been determined relative to two sets of spectral line groups in the v₁ and v₅ band, using tunable diode laser spectroscopy. Simultaneous detection using a dual-diode instrument with a absorption cell was employed to assure identical H₂CO column density for the two spectral regions. The results in the selected regions of this study are in good agreement with the line positions and the relative intensities specified in an unpublished complete line listing for the v₂ band prepared by Linda Brown (see full text for reference). Based upon measurements of individual groups of spectral lines in the P, Q and R branches, the absolute band strength has been determined to be .     

苯并氧化呋咱稳定性和异构化的DFT和ab initio研究

运用B3LYP/6-31G(d)密度泛函理论（DFT）方法对苯并氧化呋咱、邻二亚硝基苯及其间的异构化反应进行了计算研究。结果表明,苯并氧化呋咱的分子总能量比邻二亚硝基苯的低;由苯并氧化呋咱异构为邻二亚硝基苯的正向反应活化能（Ea+=51.0kJ/mol）,与文献实测值（58.6kJ/mol）较接近,而其逆向反应活化能（Ea-=4.6kJ/mol）很小,从而揭示了苯并氧化呋咱比邻二亚硝基苯更稳定·此外,进行了HF/3-21G、HF/6-31G(d)和MP2/6-31G(d)//6-31G(d)水平下相应的计算,发现B3LYP-DFT的结果较abinitio为优。谐振动频率的B3LYP/6-31G(d)计算还支持了邻二亚硝基苯为苯并氧化呋咱“自-自”互变重排反应的中间体。     

ICP－AES同时测定土壤和沉积物中全硼与其它微量及常量元素

本文阐述了用Ｈ３ＰＯ４、ＨＦ、ＨＮＯ３及ＨＣｌＯ４消化土壤及水系沉积物样品。其中磷酸的作用是避免在样品消化过程中硼的挥发损失。应用电感耦合等离子体发射光谱（简称ＩＣＰ－ＡＥＳ）同时测定样品中全硼及其它微量、常量元素的含量。该法具有高的准确度及精密度。方法快速、简便、适合土壤和沉积物的多元素测定。     

HeICl络合物的振动预离解：含时黄金规则波包研究

用含时黄金规则波包法计算了ＨｅＩＣｌｖａｎ ｄｅｒ Ｗａａｌｓ络合物分子的振动了解寿命和离解碎片ＩＣｌ的终转动态分布。并与实验和其他理论计算帮了比较。波包计算所用的总传播时间实际上是解离碎片在振动退激发绝热势能面上的滞留时间。终态相互作用对终转动态分布起着决定性作用。并预言了ＨｅＩＣｌ终转动态分布对振动态的依赖。