M6^0，±（M=Os，Ir，Pt）团簇结构与性质的密度泛函理论研究

采用密度泛函理论（DFT）中的杂化密度泛函（B3LYP）方法,在LANL2DZ基组水平上对M6^0,±（M=Os,Ir,Pt）团簇的各种可能构型进行了几何结构优化,得出各团簇的最稳定构型,并对其能量、振动频率、热力学性质、核独立化学位移（NICS）和极化率进行了理论研究．结果表明,M6^0,±（M=Os,Ir）团簇的基态都是三棱柱结构,％团簇的基态是平面三角形结构;M6^0,±（M=Os,Ir,Pt）团簇生成焓都为负值,热力学上是稳定的;NICS值都为负值,表明M6^0,±（M=Os,Ir,Pt）团簇都具有芳香性,其中Os6^-团簇的芳香性最强;从光谱分析来看,Os6的IR和Raman谱的较强吸收峰的个数最多,Ir6的IR和Raman谱的最强吸收峰都只有一个,IR最强吸收峰在137．0和143．5cm^-1之间,Raman谱最强的吸收峰位于169．5cm^-1处;Pt6的IR和Raman谱的最强吸收峰分别位于50．2和194．7cm^-1处．     

固态多环芳烃化合物的THz时域光谱研究

利用太赫兹时域光谱技术室温下对芳烃化合物萘、联苯、葸、α-萘酚和β-萘酚在3-73cm^-1(0．1．2．2THz)频谱范围内进行了光谱测量。结果表明，多环芳烃化合物在此波段有不同的吸收特征。不能形成氢键的萘、联苯和蒽在67cm^-1(2．0THz)附近均有一吸收峰，这可能是由于分子之间的振动即晶格振动所引起的；而能够形成氢键的口一萘酚和卢．萘酚，其吸收峰可归结于分子间氢键的相互作用所引起的集体振动模式。1Hz时域光谱不仅能够鉴别分子结构存在微小差别的化合物而且还能鉴别同分异构体。     

苄基化壳聚糖溶致液晶的临界浓度

用不同的方法分别合成了N 苄基化壳聚糖和N ,O 苄基化壳聚糖 ,取代度分别为 0 2 0和 0 54。用偏光显微镜测定在甲酸溶液中的液晶临界浓度。这两种聚合物的临界浓度均为 1 1wt% ,说明取代度和取代位置都不影响该体系的临界浓度值     

3,4,5-三甲氧基苯甲酸酯化壳聚糖的紫外吸收性能研究

将壳聚糖在甲磺酸中充分溶胀后,与3,4,5-三甲氧基苯甲酰氯反应,得到壳聚糖改性高分子紫外 线吸收剂。FTIR的表征表明:与壳聚糖相比,改性产物的红外谱图中1 720 cm-1处归属于C=O伸缩振动和 1 160 cm-1处归属于C-O-C对称伸缩振动的吸收峰显著增强,表明了酯化反应的发生。紫外光谱表明:产 物在220nm和274nm处具有较强的吸收峰。通过元素分析计算出不同投料比下所得改性产物的取代度,并 结合紫外光谱测试所得的数据,计算出了改性产物在273 nm处的摩尔消光系数e为8 205.9 L／(mol·cm)。     

La2CaBl0O19：Ce3＋在VUV-Vis范围的发光性质研究

通过研究La2CaB10O19:Ce3 在VUV-Vis范围的光谱，发现Ce3 在La2CaBl0O19中共有两种格位．分别取代了十配位的La3 和八配位的Ca2 ．从而发射光谱中没有出现特征的双峰。而出现了峰值约位于307．330和356nm的3个发射峰．由于在低对称性晶体场中d轨道的分裂．激发光谱中位于194，224,243,260,274和318nm的峰是由两个格位的Ce3 的f-d跃迁引起的．Ce^3 占据两个格位．可以通过以Eu3 为荧光探针的发射光谱中出现的两个5Do-7Fo跃迁得到验证．峰值位于162nm的激发谱带是基质吸收带．与基质禁带宽度相对应．通过计算．不排除其中包含O2-→Ce3 的电荷迁移带的可能性．     

2-吡啶甲醛改性壳聚糖的合成及螯合性能的研究Ⅰ.溶剂和pH值对合成及螯合性能的影响

以壳聚糖和2-吡啶甲醛为原料,合成了具有高螯合性能的2-吡啶甲醛缩壳聚糖（PYCTS）.缩合反应的最佳条件：溶胀温度为65℃,反应物配比（壳聚糖与2-吡啶甲醛的摩尔比）为1/4,溶液pH值为6.0,反应时间为12h.最高缩合率为97.5%.产品进行了红外光谱分析（1 651cm^-1出现-C=N的强特征吸收峰,1 588cm^-1,1 462cm^-1出现吡啶环的骨架振动吸收峰,768cm^-1出现吡啶环的γ＝C-H弯曲振动的强吸收峰）.并研究了PYCTS对Cu（Ⅱ）、Ni（Ⅱ）、Co（Ⅱ）、Fe（Ⅲ）离子的静态螯合性能,以及介质种类、介质酸度、金属离子浓度和螯合时间对PYCTS螯合金属离子能力的影响.结果表明：在pH为3～8时,其对Cu（Ⅱ）、Ni（Ⅱ）、Co（Ⅱ）具有较好的螯合性能,且介质种类和介质酸度对PYCTS螯合金属离子能力的影响较大.     

二甲基二烯丙基氯化铵及其聚合物的红外光谱研究

对二甲基二烯丙基氯化铵（DMDAAC）不同聚合度的均聚物和它与丙烯酰胺的共聚物进行了结构分析，讨论了红外光谱吸收峰随聚合物特性粘度、单体的质量分数变化的规律及原因。结果表明，在均聚物中，随粘度的升高，峰位分别为1262cm^-1和678cm^-1处的碳氮键的伸缩与变形振动吸收峰增强；在共聚物中，当粘度不是很大时，粘度或单体的质量分数的升高都会使3017cm^-1处碳氢键的伸缩振动吸收峰增强。     

红外光谱法测定干酪素与丙烯腈接枝共聚物的组成

以干酪素vc-o的特征吸收峰(1244cm^-1)和丙烯腈vcmN的特征吸收峰(2244cm^-1)为测定波长,利用二者的吸光度比值与干酪素和丙烯腈接枝共聚物中丙烯腈的百分含量呈线性的关系,建立了利用红外光谱测定干酪素与丙烯腈接枝共聚物组成的方法,线性范围为22％～54％,相关系数r=0．9911,相对标准偏差(RSD)为1．50％。该法简便、快速,有良好的稳定性。     

四-（4-吡啶基）卟啉二酸聚集体的共振拉曼光谱

研究了近激子吸收带激发下四-（4-吡啶基）卟啉二酸（H8TPyP^6＋）聚集体的共振拉曼光谱。测量了H8TPyP^6＋单体和聚集体的紫外可见吸收谱和共振光散射光谱．在氘代位移的基础上结合相关体系振动光谱研究,对测得的H8TPyP^6＋单体和聚集体的拉曼谱带进行了指认．聚集体的形成导致H8TPyP^6＋的卟啉环CC／CN面内伸缩振动向低波数方向位移2-6cm^-1,而卟啉环鞍形面外振动带向高波数方向位移12cm^-1．基于拉曼谱带的强度和频率变化分析了聚集引起的H8TPyP^6＋分了内结构变化和分子间氢键作用．     

钛硅分子筛挤条成型催化剂热稳定性能的研究

采用在空气中程序升温焙烧的方式考察了钛硅分子筛挤条成型催化剂的热稳定性能．对不同温度焙烧得到的样品进行了XRD、IR、UV Raman和SEM表征．结果表明，在高温焙烧时，由于载体结构的改变引起载体与分子筛之问相互作用发生变化，导致成型催化剂中分子筛骨架破坏．随着焙烧温度的提高，IR谱图中960cm^-1处代表钛进入骨架的特征峰的强度迅速减弱，当焙烧温度达到1000℃时，960cm-1处的骨架钛特征峰移至948cm^-1．在紫外拉曼谱图中，骨架位钛物种的特征拉曼谱峰-1125cm^-1谱峰在加入SiO2载体后，高温下峰强度明显降低，这说明载体的加入降低了钛硅分子筛挤条成型催化剂的热稳定性能．     

FT-Raman spectroscopy - analytical tool for routine analysis of diazinon pesticide formulations

FT-Raman spectroscopy based on band intensity and band area measurements, was used for the quantitative determination of diazinon in pesticide formulations. Bands at 554, 604, 631, 1562 and 2971 cm(-1) were used for calibration. Spectra were acquired by averaging 100 scans at a resolution of 4 cm(-1). Calibration curves were linear (correlation coefficients, 0.992-0.9992 and 0.99-0.999 for band intensity and band area measurements, respectively) in the range of 0.2-3.5 M for 554 and 2971 cm(-1), 0.3-3.5 M for 604 cm(-1), 0.6-3.5 M for 1562 cm(-1) and 1.0-3.5 M for 631 cm(-1) bands. Normalization of calibration curves against the 802 cm(-1) cyclohexane band improved their long term stability and minimized the effect of laser beam power fluctuations. No interference was found by commonly used surfactants and the proposed method was applied to the analysis of diazinon formulations. Results obtained compare well as indicated by the t-test, with those obtained by the HPLC reference method. Precision ranged between 0.2-7.8 and 0.1-7.2% RSD, (n=4) for band intensity and band area measurements, respectively. The proposed method is rapid, simple and safe, as toxic samples are analyzed 'as received' without sample pre-treatment, permiting the routine analysis of pesticides formulations.     

Infrared and infrared emission spectroscopy of the zinc carbonate mineral smithsonite

Infrared emission and infrared spectroscopy has been used to study a series of selected natural smithsonites from different origins. An intense broad infrared band at 1440cm(-1) is assigned to the nu(3) CO(3)(2-) antisymmetric stretching vibration. An additional band is resolved at 1335cm(-1). An intense sharp Raman band at 1092cm(-1) is assigned to the CO(3)(2-) symmetric stretching vibration. Infrared emission spectra show a broad antisymmetric band at 1442cm(-1) shifting to lower wavenumbers with thermal treatment. A band observed at 870cm(-1) with a band of lesser intensity at 842cm(-1) shifts to higher wavenumbers upon thermal treatment and is observed at 865cm(-1) at 400 degrees C and is assigned to the CO(3)(2-)nu(2) mode. No nu(2) bending modes are observed in the Raman spectra for smithsonite. The band at 746cm(-1) shifts to 743cm(-1) at 400 degrees C and is attributed to the CO(3)(2-)nu(4) in phase bending modes. Two infrared bands at 744 and around 729cm(-1) are assigned to the nu(4) in phase bending mode. Multiple bands may be attributed to the structural distortion ZnO(6) octahedron. This structural distortion is brought about by the substitution of Zn by some other cation. A number of bands at 2499, 2597, 2858, 2954 and 2991cm(-1) in both the IE and infrared spectra are attributed to combination bands.     

Determination of the carbonyl groups in native lignin utilizing Fourier transform Raman spectroscopy

A near-infrared Fourier transform Raman (NIR-FTR) spectroscopic technique was utilized to determine the chemical structure of lignin in a woody matrix. In the NIR-FTR spectra of coniferaldehyde and coniferyl alcohol, the Raman bands for the carbonyl group and the alpha, beta unsaturated bond were detected at 1620 and 1660 cm(-1), respectively. These peaks were also found in the NIR-FTR spectra of chemically synthesized lignins, isolated lignin from conifer wood, and conifer wood meal. Upon the reduction of carbonyl groups in the lignin samples and wood meal, the band at 1620 cm(-1) disappeared; on the other hand, the band at 1660 cm(-1) remained unchanged. However, upon the oxidation of reduced lignin at the benzyl hydroxyl group using dicyanodichrolobenzoquinone, the band at 1620 cm(-1) clearly appeared, strongly suggesting that the band at 1620 cm(-1) can be assigned as a carbonyl marker band. The hydrogenation reaction optimized for the reduction of the unsaturated bond in lignin caused the disappearance of the band at 1660 cm(-1), indicating that the band at 1660 cm(-1) is an alpha, beta unsaturated bond marker band. The change in carbonyl content during the wood decay process was also shown to be monitored using the Raman intensity of the carbonyl marker band. It was indicated that the NIR-FTR spectroscopic techniques were suitable analytical method for a rapid and nondestructive analysis of wood samples.     

Raman spectroscopy of the mineral rhodonite

The mineral rhodonite an orthosilicate has been characterised by Raman spectroscopy. The Raman spectra of three rhodonites from Broken Hill, Pachapaqui and Franklin were compared and found to be similar. The spectra are characterised by an intense band at around 1000 cm(-1) assigned to the nu(1) symmetric stretching mode and three bands at 989, 974 and 936 cm(-1) assigned to the nu(3) antisymmetric stretching modes of the SiO(4) units. An intense band at around 667 cm(-1) was assigned to the nu(4) bending mode and showed additional bands exhibiting loss of degeneracy of the SiO(4) units. The low wave number region of rhodonite is complex. A strong band at 421.9 cm(-1) is attributed to the nu(2) bending mode. The spectra of the three rhodonite mineral samples are similar but subtle differences are observed. It is proposed that these differences depend upon the cationic substitution of Mn by Ca and/or Fe(2+) and Mg.     

Effect of mordenite dealumination on the structure of encapsulated molybdenum catalysts

A series of dealuminated mordenites treated under various conditions of acid leaching was impregnated in an aqueous solution of ammonium heptamolybdate to achieve a loading of 12 wt% Mo. These samples were characterized by XRD, UV-DRS, N(2) adsorption, TGA, and FTIR techniques. Special attention was given to the far-IR measurements and IR study of surface hydroxyl groups before and after dealumination. A polymolybdate species was recognized by the appearance of bands at 344, 319, and 236 (229) cm(-1) due to the vibrational modes of delta(Mo-O) and delta(Mo-O-Mo), respectively. The disappearance of the 236 cm(-1) band as well as that at 344 cm(-1) in favor of the 319 cm(-1) band, with the dealumination, was related to the high dispersion of Mo species in the produced mesopore surface assessed by the N(2) adsorption at 77 K. No bands due to bulk MoO(3) were detected from the IR and XRD results. A strong interaction between Mo species and dealuminated mordenite surfaces (OH groups) was recognized by a decrease in intensity and a marked shift of the band at 3745 to 3727 cm(-1) as well as the appearance of a new band at 3668 cm(-1). The latter band was produced by the interaction of the framework Al-OH with Mo species. The BET surface areas of Mo-dealuminated mordenite samples were higher than the corresponding Mo-free ones. The diffuse reflectance measurements suggested that Mo cations are predominantly present as an octahedrally coordinated Mo(6+), along with some tetrahedral Mo(6+). New spectral features as a consequence of dealumination events in the far-IR range were evaluated and discussed.     

FTIR studies of plasticized poly(vinyl alcohol)-chitosan blend doped with NH4NO3 polymer electrolyte membrane

Fourier transform infrared (FTIR) spectroscopy studies of poly(vinyl alcohol) (PVA), and chitosan polymer blend doped with ammonium nitrate (NH(4)NO(3)) salt and plasticized with ethylene carbonate (EC) have been performed with emphasis on the shift of the carboxamide, amine and hydroxyl bands. 1% acetic acid solution was used as the solvent. It is observed from the chitosan film spectrum that evidence of polymer-solvent interaction can be observed from the shifting of the carboxamide band at 1660 cm(-1) and the amine band at 1591 cm(-1) to 1650 and 1557 cm(-1) respectively and the shift of the hydroxyl band from 3377 to 3354 cm(-1). The hydroxyl band in the spectrum of PVA powder is observed at 3354 cm(-1) and is observed at 3343 cm(-1) in the spectrum of the PVA film. On addition of NH(4)NO(3) up to 30 wt.%, the carboxamide, amine and hydroxyl bands shifted from 1650, 1557 and 3354 cm(-1) to 1642, 1541 and 3348 cm(-1) indicating that the chitosan has complexed with the salt. In the PVA-NH(4)NO(3) spectrum, the hydroxyl band has shifted from 3343 to 3272 cm(-1) on addition of salt from 10 to 30 wt.%. EC acts as a plasticizing agent since there is no shift in the bands as observed in the spectrum of PVA-chitosan-EC films. The mechanism of ion migration is proposed for the plasticized and unplasticized PVA-chitosan-NH(4)NO(3) systems. In the spectrum of PVA-chitosan-NH(4)NO(3)-EC complex, the doublet CO stretching in EC is observed in the vicinity 1800 and 1700. This indicates that there is some interaction between the salt and EC.     

Emission spectra of HCN/HNC in the 2-5 microm range of astrophysical interest

Emission from H12C14N observed with a Fourier transform spectrometer from a radio-frequency excited plasma is reported in the 2400-3400 cm(-1) spectral range of astrophysical interest. The molecular constants, for 21 vibration-rotation bands are given, as well as estimates of the first-order Herman-Wallis coefficients for 11 bands. These constants are derived from about 900 observed transitions in HCN, and are used to generate a sequential linelist of about 1400 calculated line positions, within a standard deviation equal to 3 x 10(-4) cm(-1). The relative intensities of the observed lines are also reported, as well as those for the nu1 band of H14N12C, at 3650 cm(-1), simultaneously observed from the same plasma.     

Characterization of low-frequency modes in aqueous peptides using far-infrared spectroscopy and molecular dynamics simulation

Far-infrared spectroscopy was used to study the dynamics of three aqueous peptides having varied helicity. Experimental data were compared to the molecular dynamics simulated far-infrared absorbance spectrum derived from the dipole time correlation function. Vibrational density of state (VDOS) simulation was then used to analyze the contribution of different structural elements to the bands. Frozen aqueous peptide samples were studied in the frequency range between 325 and 540 cm(-1) where the ice absorbance is low. Three resonances were identified; band I centered at approximately 333 cm(-1), band II centered at approximately 380 cm(-1), and band III comprising two constituent bands at approximately 519 and 528 cm(-1). The peak height and frequency of the maximum absorbance of bands I and II varied depending on the helicity of the peptide. VDOS of the far-infrared absorbance spectrum confirmed that bands I and II were associated with the peptide backbone and that band III had both potential backbone and side chain components.     

Characterisation of Ni silicate-bearing minerals by UV-vis-NIR spectroscopy. Effect of Ni substitution in hydrous Ni-Mg silicates

Three Ni silicate-bearing pimelite, nepouite and pecoraite minerals, from Australia have been investigated by UV-vis-NIR spectroscopy to study the effect of Ni-Mg substitution. The observation of three major absorption bands at 9205-9095, 15,600-15,190 and 26,550-25,660 cm(-1) are the characteristic features of Ni(2+) in sixfold coordination. The effect of cation substitution like Mg(2+) for Ni(2+) on band shifts in electronic and vibrational spectra enable the distinction between the Ni-bearing silicates.     

High resolution FTIR spectrum of the nu1 band of DCOOD

Accurate spectral information on formic acid has wide application to radioastronomy since it was the first organic acid found in interstellar space. In this work, the infrared absorption spectrum of the nu1 band of deuterated formic acid (DCOOD) has been measured on a Bomem DA3.002 Fourier transform spectrometer in the wavenumber region 2560-2690 cm(-1) with a resolution of 0.004 cm(-1). A total of 292 infrared transitions have been assigned in this hybrid type A and B band centred at 2631.8736 +/- 0.0004 cm(-1). The assigned transitions have been fitted to give a set of eight rovibrational constants for the nu1 = 1 state with a standard deviation of 0.00078 cm(-1).