Decontamination of the chemical warfare agent simulant dimethyl methylphosphonate by means of large-area low-temperature atmospheric pressure plasma

Dimethyl methylphosphonate (DMMP), a chemical simulant of the nerve gas GB, was decontaminated with a nonthermal atmospheric pressure plasma. The decontamination efficiency was measured qualitatively by means of Fourier transform spectroscopy and quantitatively by means of gas chromatography. With helium gas only, 10 g/m² of DMMP on an aluminum surface was 99.9% decontaminated in 2 min, furthermore, with the addition of 5% of oxygen gas, it was 99.99% decontaminated in 10 min. Given the low input power (<100 W) and temperature (<75 °C), this plasma is eligible for nondestructive decontamination of almost all material surfaces.     

Reanalysis of the microwave absorption spectrum of dimethyl methylphosphonate and its internal rotation problem

The Fourier transform microwave spectrum of dimethyl methylphosphonate studied by us previously is reanalyzed here to obtain more physically reasonable parameters describing the various Coriolis-like couplings between overall rotation and internal rotation of the two methoxy methyl tops. In particular, we use exactly the same frequencies and spectral assignments as in our previous study, but the least squares fit is started from a rather different set of initial molecular parameters and is carried out with a slightly smaller set of adjustable parameters. The standard deviation of the fit is not significantly changed, but convergence to a rather different minimum in parameter space is obtained. This new minimum does not change the three rotational constants significantly, but values for the 12 Coriolis coupling constants are dramatically rearranged, so that parameters arising from coupling between the two internal rotation motions are greatly reduced in magnitude. These new Coriolis constants bring the derived direction cosines for the methoxy methyl groups in the principal axis system into much better agreement with ab initio predictions. We have used our new parameters to derive internal rotation barrier heights for the two methyl groups of 280 and 188 cm⁻¹.     

Line assignments and global analysis of the tunneling-rotational microwave absorption spectrum of dimethyl methylphosphonate

Line assignments were carried out for about 600 Fourier-transform microwave transitions for dimethyl methylphosphonate involving levels of all six symmetry species in the G₁₈ molecular symmetry group appropriate for three large-amplitude motions and covering J and K values of 1?J?6 and 0?|K|?3. The assignments are based on combination-difference loops, variations in line shape for different symmetry species caused by the small internal-rotor splitting patterns of the third, high-barrier methyl top, and agreement with theoretically expected positions. A global fit of 609 lines to a phenomenological tunneling-rotational Hamiltonian with 54 constants was performed, yielding a standard deviation of 8.0 kHz, which is close to the experimental measurement uncertainty. The A/E tunneling splitting for the lowest barrier methyl group internal rotation motion was determined indirectly to be about 34 GHz. The much smaller tunneling splitting for the methoxy interchange motion was determined (with some assumptions) to be 3.3 MHz.     

Interaction of dimethyl methylphosphonate with oxidized iron and the effect of coadsorbed water

The behavior of dimethyl methylphosphonate (DMMP), dosed at 100 K with and without coadsorbed water on oxidized iron has been examined by temperature programmed desorption (TPD) and Auger electron spectroscopy (AES). Molecular and dissociated states of DMMP are readily distinguished by the P(LMM) Auger lineshape. At low coverages DMMP undergoes complete decomposition during heating, leaving carbon, phosphorus and oxygen residues on the surface. The major low temperature decomposition products are CH₃OH, H₂O, CO, H₂ and a surface phosphate species. The DMMP decomposition is limited and large exposures lead to molecular DMMP desorption characteristics of multilayers (200–210 K). Pre-exposure to H₂O increases the extent of DMMP decomposition.     

Mid-infrared absorption cross-sections and temperature dependence of CFC-113

The temperature dependence of the infrared absorption cross-sections of CFC-113 (1,1,2-trichlorotrifluoroethane) in a pure vapor phase has been recorded in the 600-1250 cm⁻¹ spectral region using Fourier transform spectroscopy. Spectra at 0.05 cm⁻¹ resolution have been used to derive the integrated band strengths of the five main absorption bands over a range of temperatures from 223 to 283 K. Our results show good agreement with previously published data. The new cross-sections will allow more accurate retrieval of atmospheric CFC-113 concentrations using infrared spectroscopic techniques.     

Theory of line shape of optical absorption and emission spectra in molecular crystals

We solve the equations of the coupled coherent and incoherent motion of excitons in molecular crystals and determine the optical line shapes and positions including Davydov splitting.     

香荆芥酚的荧光光谱和吸收光谱研究

研究了中药活性成分香荆芥酚(Carvacrol)的荧光光谱和吸收光谱,依据光谱数据测量了香荆芥酚的电离常数和荧光量子产率.在pH＜2.0时,香荆芥酚的荧光随溶液pH增大而增强;在pH2.0～8.0范围内,香荆芥酚有稳定的强荧光,最大激发波长为278 nm,最大发射波长为306 nm; pH＞8.0时荧光强度随pH的增大...     

Analytical derivation of interference dips in molecular absorption spectra: molecular properties and relationships to Fano's antiresonance

An analytical expression is derived for the decrease in the absorption cross section that occurs when two molecular electronic states are coupled by spin-orbit coupling. The loss of intensity, or interference dip, is common in the spectra of metal compounds. The derivation is based on a coupling of a single forbidden donor state to a broadened harmonic acceptor potential, and leads to simple analytical expressions. The new expressions give line shape functions different from those in the commonly used Fano antiresonance interpretation and are based on interpretable molecular properties.     

Impact of molecular tilt angle on the absorption spectra of pentacene:perfluoropentacene blends

We investigate the relation between the optical properties and the average molecular tilt angle for blends of pentacene and perfluoropentacene, which can be considered as a prototypical donor–acceptor complex. Combining near‐edge X‐ray absorption fine‐structure spectroscopy and optical spectroscopy we study thin films of these compounds prepared at three different substrate temperatures T_sub. For T_sub =180 K we observe a larger average tilt angle than for blends prepared at higher substrate temperatures. This orientational change has significant impact on the uniaxial anisotropic optical properties of the mixed films which we measure post growth as well as in real‐time during growth. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

等离子体X射线吸收谱及发射谱研究

 报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法；该方法基于相对论原子理论，可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）；应用了量子亏损理论，可以减少计算量。利用该方法计算金等离子体LTE吸收谱，计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。     

等离子体X射线吸收谱及发射谱研究

报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法;该方法基于相对论原子理论,可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）;应用了量子亏损理论,可以减少计算量。利用该方法计算金等离子体LTE吸收谱,计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。     

Terahertz absorption spectra of nitromethane

Nitromethane, with its heavy frame and internal rotator, readily evaporates into the atmosphere making it an ideal candidate for remote sensing. Here we present the absorption spectra of gas-phase nitromethane between 9 and 50 cm⁻¹. Measurements were taken using a Bruker IFS 66v Fourier transform far-infrared (FTIR) spectrometer at a resolution of 0.12 cm⁻¹ (0.0036 THz) from 9 to 40 cm⁻¹ and a Bruker Vertex 80v FTIR spectrometer with a resolution of 0.0075 cm⁻¹ (0.00226 THz) from 10 to 50 cm⁻¹. The absorption spectra were measured at multiple pathlengths ranging from 2 to 6 m. These measurements were used to calculate the absorption coefficient of nitromethane as a function of wavenumber.     

Polarized absorption spectra of diphenylnitroxide

A polarization study of the low-lying electronic states of the diphenylnitroxide radical imbedded in a benzophenone single crystal is presented. Assignments are made for the first two electronic excited states: ${}^2\text{B}{}_2\text{(n → π}{}^1\text{)}$ at 569 nm and ${}^2\text{B}{}_1\text{(π → π}{}^1\text{)}$ at 431 nm. Vibronic coupling is invoked in inducing the $\text{n → π}{}^1$ transition. The electronic structure of the nitroxide bears some resemblance to the corresponding carbonyl. The delocalization of the π electrons is also discussed.     

Mid-infrared high-resolution absorption spectroscopy by use of a semimonolithic entangled-cavity optical parametric oscillator

By recording low-pressure absorption lines of N2O around 3.9 microm, we fully qualify a pulsed entangled-cavity doubly resonant optical parametric oscillator as a power tool for high-resolution spectroscopy. This compact source runs at a high repetition rate (>10 kHz) with a low threshold of oscillation (<8 microJ), is mode-hop-free tunable over 5 cm(-1), and displays single-frequency Fourier-transformed-limited operation (linewidth <0.005 cm(-1)). A high potential for nonlinear spectroscopy is also expected given the high peak power (70 W) and the good quality (M2 < 2) of the output beam.     

Optical absorption spectra of I3 - molecular ions in KI crystals and aqueous solutions

A semiempirical molecular orbital method including spin-orbit interaction is used to study optical absorption spectra of I₃ ^- molecular ions in (KI + I₂) aqueous solutions and in KI crystals coloured additively or electrolytically. The splitting of two strong absorption bands observed for these specimens is considered to be due to the spin-orbit interaction in the iodine atoms. The values of the spin-orbit coupling constants for I₃ ^- in aqueous solutions and coloured KI crystals are estimated to be 0·56 and about 0·47 eV, respectively. The oscillator strengths of the two strong bands for these specimens is also discussed.     

IR absorption spectra of molecular anions in CsI-CO3 and CsI-Tl,CO3 crystals

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 52, No. 1, pp. 44–47, January, 1990.     

Low-temperature optical absorption spectra of hematoporphyrins

Low-temperature optical absorption spectra of both free base and metal complexes of hematoporphyrin have been obtained. Vibrational structure, inferred by others from MORD data, is observed here directly in bands III and IV of the free base. Structure is also observed in the β band of the Ni and Pd metallohematoporphyrins. Implications of these results on the presently accepted theory of porphyrin optical spectra are discussed.     

IR absorption spectra of N-substituted tetrazoles

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 6, pp. 923–933, June, 1991.