Semi-empirical calculation of air-broadened half-widths and air pressure-induced frequency shifts of water-vapor absorption lines

This paper describes a semi-empirical calculation of the air-broadened half-widths and the air pressure-induced frequency shifts for the H₂¹⁶O isotopologue. This semi-empirical calculation is based on fits of several recent high-quality measurements and theoretical calculations to the first-order terms in the expansion of the complex Robert-Bonamy (CRB) equations, which yields a second- and first-order polynomial function of the differences in the upper- and lower-state vibrational quantum numbers for the half-width and line shift, respectively. The aim of this work was to obtain a complete set of air-broadened half-widths and air pressure-induced frequency shifts for transitions of H₂¹⁶O present in the HITRAN database from microwave to the visible in order to supplement the observed and calculated values. For around 700 sets of rotational quantum numbers (), semi-empirical coefficients describing the vibrational dependence of the air-broadened half-widths and the air pressure-induced frequency shifts have been obtained directly from the fit of experimental and/or theoretical data. The accuracy of the parameters deduced from this calculation is estimated to be between 5% and 10% for the air-broadened half-widths and between 0.001 and for the air pressure-induced frequency shifts. For sets of rotational quantum numbers for which either none or insufficient experimental/theoretical data were available to deduce a vibrational dependence, further approximations have been used to obtain a complete set of semi-empirical coefficients.     

The water-vapor continuum and selective absorption in the 3-5 μm spectral region at temperatures from 311 to 363 K

The pure water-vapor continuum absorption in the 2.88 to 5.18 μm spectral region has been measured using a Fourier-transform infrared spectrometer at a resolution of 0.1 cm⁻¹. The sample temperatures and pressures varied from 311 to 363 K and from 2.8 kPa (21 Torr) to 34.5 kPa (259 Torr), respectively. The path lengths used in the study ranged from 68 to 116 m. Under these conditions, the continuum absorption in the middle of the 4 μm window is quite detectable reaching as high as 4%. The spectral processing included calculations to fit and remove the H₂O ro-vibrational structure. In the region around 5 μm, the absorption coefficients obtained are in good agreement with those of the commonly used MT_CKD continuum model. However at shorter wavelengths, the observed values significantly deviate from the model. Inspection of the present data as well as that of previous measurements leads to the conclusion that the MT_CKD model despite the latest updates significantly underestimates the rate of the continuum temperature dependence over the 4 μm atmospheric window. Line strengths for 189 H₂O transitions were obtained from the spectral processing. The deviation of these measured intensities from those listed in the HITRAN database is randomly scattered around zero to within several percents and no systematic trends were detected.     

复合吸附剂SiO2·xH2O·yCaCl2的水蒸气吸附等温线

配制了一种由粗孔球形硅胶和氯化钙组成的新型复合吸附剂SiO2·xH2O·yCaCl2,测得了4个不同氯化钙含量的复合吸附剂样品(氯化钙质量分数分别为0.130,0.2733,0.384和0.510)、CaCl2和粗孔球形硅胶在25℃、35℃及45℃的水蒸气吸附等温线。实验结果表明,复合吸附剂的平衡吸水量随CaCl2质量分数增加而增加,最大可达到粗孔球形硅胶的10倍。用Dubinin-Astakhov方程回归测得的等温线,求得相应的参数。     

小叶女贞花挥发性成分分析

采用水蒸汽蒸馏法,分别以正己烷和乙醚为萃取剂从小叶女贞花中提取挥发性成分,结合气相色谱-质谱(GC-MS)法,运用峰面积归一化法计算各化学成分在挥发油中的相对含量.在正己烷萃取的挥发油中鉴定了45种组分,在乙醚萃取的挥发油中鉴定了58种组分.研究了不同极性溶剂作萃取剂对小叶女贞花挥发性成分的影响.     

聚酯聚氨酯透气性的正电子研究

用正电子湮没寿命谱(PALS)研究了温度和PEG含量对以聚己二酸丁二醇酯(PBA)为软段的聚酯聚氨酯的自由体积特性和透气性的影响.实验结果表明,自由体积空洞的体积随着温度的升高而增加,分布变宽,导致透气性增大.不同PEG含量的聚酯聚氨酯PBA-10,PBA-15和PBA-20的水汽渗透系数(WVP)基本相同.结果表明,在这类聚氨酯中,影响透气性的主要因素不仅是自由体积,而且与材料的亲水性有关.     

A first principles simulation study of fluctuations of hydrogen bonds and vibrational frequencies of water at liquid-vapor interface

We present a theoretical study of the structure and dynamics of water-vapor interface by means of ab initio molecular dynamics simulations. The inhomogeneous density, hydrogen bond and orientational profiles, voids and vibrational frequency distributions are investigated. We have also studied various dynamical properties of the interface such as diffusion, orientational relaxation, hydrogen bond dynamics and vibrational frequency fluctuations. The diffusion and orientational relaxation of water molecules are found to be faster at the interface which can be correlated with the voids present in the system. The hydrogen bond dynamics, however, is found to be slightly slower at the interface than that in bulk water. The correlations of hydrogen bond relaxation with the dynamics of vibrational frequency fluctuations are also discussed.