CH5+: the infrared spectrum observed

Protonated methane, CH5+, has unusual vibrational and rotational behavior because its three nonequivalent equilibrium structures have nearly identical energies and its five protons scramble freely. Although many theoretical papers have been published on the quantum mechanics of the system, a better understanding requires spectral data. A complex, high-resolution infrared spectrum of CH5+ corresponding to the C-H stretching band in the 3.4-micrometer region is reported. Although no detailed assignment of the individual lines was made, comparison with other carbocation spectra strongly suggests that the transitions are due to CH5+.     

Understanding the infrared spectrum of bare CH5+

Protonated methane, CH5+, continues to elude definitive structural assignment, as large-amplitude vibrations and hydrogen scrambling challenge both theory and experiment. Here, the infrared spectrum of bare CH5+ is presented, as detected by reaction with carbon dioxide gas after resonant excitation by the free electron laser at the FELIX facility in the Netherlands. Comparison of the experimental spectrum at approximately 110 kelvin to finite-temperature infrared spectra, calculated by ab initio molecular dynamics, supports fluxionality of bare CH5+ under experimental conditions and provides a dynamical mechanism for exchange of hydrogens between CH3 tripod positions and the three-center bonded H2 moiety, which eventually leads to full hydrogen scrambling. The possibility of artificially freezing out scrambling and internal rotation in the simulations allowed assignment of the infrared spectrum despite this pronounced fluxionality.     

Quantum deconstruction of the infrared spectrum of CH5+

We present two quantum calculations of the infrared spectrum of protonated methane (CH5+) using full-dimensional, ab initio-based potential energy and dipole moment surfaces. The calculated spectra compare well with a low-resolution experimental spectrum except below 1000 cm(-1), where the experimental spectrum shows no absorption. The present calculations find substantial absorption features below 1000 cm(-1), in qualitative agreement with earlier classical calculations of the spectrum. The major spectral bands are analyzed in terms of the molecular motions. Of particular interest is an intense feature at 200 cm(-1), which is due to an isomerization mode that connects two equivalent minima. Very recent high-resolution jet-cooled spectra in the CH stretch region (2825 to 3050 cm(-1)) are also reported, and assignments of the band origins are made, based on the present quantum calculations.     

基于田间原位土壤含水量估测的可见/近红外光谱建模方法

为实时、准确地获取原位土壤含水量信息,利用可见/近红外光谱技术,分别使用全局偏最小二乘(PLS)建模、局部PLS建模方法,对田间原位土壤含水量进行快速估测。结果表明:全局PLS模型中,其建模集的决定系数(R~2)、交叉验证均方根误差(RMSECV)分别为0.943和1.750%,检验集的决定系数(R~2)、预测均方根误差(RMSEP)分别为0.956和1.260%。局部PLS模型中,分别比较了选取定标子集的2种方法(欧氏距离法和马氏距离法),采用欧氏距离法和马氏距离法选取定标子集进行建模的R~2值分别为0.974和0.979,RMSEP值分别为0.976%和0.943%。因此,将可见/近红外光谱技术应用到田间原位含水量测量是可行的,其中,使用局部建模方法的效果优于全局建模。     

Infrared spectroscopic evidence for protonated water clusters forming nanoscale cages

Size-dependent development of the hydrogen bond network structure in large sized clusters of protonated water, H+(H2O)n (n = 4 to 27), was probed by infrared spectroscopy of OH stretches. Spectral changes with cluster size demonstrate that the chain structures at small sizes (n less, similar 10) develop into two-dimensional net structures (approximately 10 < n < 21), and then into nanometer-scaled cages (n >/= 21).     

Ultrafast hydrogen-bond dynamics in the infrared spectroscopy of water

We investigated rearrangements of the hydrogen-bond network in water by measuring fluctuations in the OH-stretching frequency of HOD in liquid D2O with femtosecond infrared spectroscopy. Using simulations of an atomistic model of water, we relate these frequency fluctuations to intermolecular dynamics. The model reveals that OH frequency shifts arise from changes in the molecular electric field that acts on the proton. At short times, vibrational dephasing reflects an underdamped oscillation of the hydrogen bond with a period of 170 femtoseconds. At longer times, vibrational correlations decay on a 1.2-picosecond time scale because of collective structural reorganizations.     

绿色快速分析技术--近红外及其应用

介绍了近红外光谱快速分析技术的特点。以其在农业、加工业和烟草等行业中的具体应用说明近红外光谱分析技术及其快速、无污染、无需前处理、非破坏性及多组分同时定量分析等优势所产生的巨大社会效益和经济效益。     

Rotationally resolved infrared spectrum of the charge transfer complex [Ar-N2]+

Difficulties in preparing cluster ions for spectroscopic studies have limited our understanding of intermolecular forces in charged complexes that are typical of many reactive intermediates. Here, the infrared spectrum of the charge transfer complex [Ar-N2]+, recorded in a supersonic planar plasma with a tunable diode laser spectrometer, is presented. More than 70 adjacent rovibrational transitions were measured near 2272 wave numbers and assigned to the molecular nitrogen stretching fundamental in the 2Sigma+ ground state of [Ar-N2]+. The accurate structural parameters that were determined confirm a linear structure and show that the major part of the charge is located at the argon atom. The latter result is surprising and implies a charge switch of the cationic center upon complexation.     

The infrared spectrum of Al2H6 in solid hydrogen

Although many volatile binary boron hydride compounds are known, binary aluminum hydride chemistry is limited to the polymeric (AlH3)(n) solid. The reaction of laser-ablated aluminum atoms and pure H2 during codeposition at 3.5 kelvin, followed by ultraviolet irradiation and annealing to 6.5 kelvin, allows dimerization of the intermediate AlH3 photolysis product to form Al2H6. The Al2H6 molecule is identified by seven new infrared absorptions that are accurately predicted by quantum chemical calculations for dibridged Al2H6, a molecule that is isostructural with diborane.     

牡蛎多肽螯合锌的制备及红外光谱分析

以牡蛎酶解多肽液和硫酸锌为原料制备牡蛎多肽螯合锌,应用中心组合试验设计对螯合反应条件进行优化,并对螯合产物进行红外光谱分析和氨基酸含量分析。结果表明:优化后的螯合参数为70.5℃、pH6.94、牡蛎酶解多肽液中氨基酸态氮与锌离子质量比为2.56:1、反应时间为20 min,在此该条件下,锌螯合率为88.25%。液相色谱分析结果表明牡蛎多肽螯合锌中必需氨基酸的百分比含量均基本符合WHO/FAO标准模式谱规定的百分比,红外光谱分析结果则表明螯合产物在2924 cm~(-1)附近有宽吸收峰,说明生成了一种新型的牡蛎多肽锌螯合物,该结果为牡蛎多肽复合产品的生产和开发提供基础性研究数据。     

Jupiter: its infrared spectrum from 16 to 40 micrometers

Spectral measurements of the thermal radiation from Jupiter in the band from 16 to 40 micrometers are analyzed under the assumption that pressure-broadened molecular hydrogen transitions are responsible for the bulk of the infrared opacity over most of this spectral interval. Both the vertical pressure-temperature profile and the molecular hydrogen mixing ratio are determined. The derived value ofthe molecular hydrogen mixing ratio, 0.89 +/- 0.11, is consistent with the solar value of 0.86.     

Theory untangles the high-resolution infrared spectrum of the ortho-H2-CO van der Waals complex

Rovibrational spectroscopy of molecules boasts extremely high precision, but its usefulness relies on the assignment of spectral features to corresponding quantum mechanical transitions. In the case of ortho-H(2)-CO, a weakly bound complex abundant in the interstellar medium (although not yet observed there), the rather complex spectrum has been unexplained for more than a decade. We assigned this spectrum by comparison with a purely ab initio calculation. For most lines, agreement to within 0.01 centimeter(-1) between experiment and theory was achieved. Our results show that the applicability of rovibrational spectroscopy can be extended with the assistance of high-accuracy quantum mechanical computations.     

Tunable infrared laser spectroscopy of atmospheric water vapor

Absorption lines in the v, band of water vapor at 6.3 micrometers have been fully resolved by using a tunable semiconductor laser. Three attnospheric water vapor lines near 5.32 micrometers were studied in detail and found to have linle widths two to four times narrower than the width calculated by Benedict and Kaplan.     

中国6种地带性土壤红外光谱特性研究

利用土壤原样研究了中国 6种典型地带性土壤的红外光谱特征。结果表明 ,砖红壤、红壤红外光谱属于高岭石型图谱 ,显著的 36 95 ,36 2 0 ,10 35 cm- 1峰以及 35 2 7cm- 1峰可作为用红外光谱判断热带、南亚热带地带性土壤的特征峰。黄棕壤、褐土、黑垆土、黄绵土红外光谱为蒙脱石型图谱 ,较弱的 36 2 1cm- 1峰 ,3435和 10 2 8～10 32 cm- 1的强宽带 ,以及显著的 14 37cm- 1峰可作为温带半湿润 -半干旱地区石灰性土壤红外光谱的特征标志。黄棕壤是石灰性土壤向热带、南亚热带地区过渡的地带性土壤 ,其红外光谱标志为较宽的 3435 ,10 32 cm- 1吸收带和明显的 36 2 0 cm- 1吸收峰 ,以及较弱的 36 95 cm- 1峰 ,但没有 14 37cm- 1峰。中国从南到北 ,土壤红外光谱的36 96 ,36 2 1cm- 1 峰、石英双峰 (798,780 cm- 1 )的 797cm- 1 峰吸收强度逐渐减弱 ,而石英双峰的 780 cm- 1 峰吸收强度逐渐增强。     

Gas-phase clusters: spanning the States of matter

Gas-phase clusters, which are weakly bound aggregates comprised of either atoms or molecules, often display properties that lie between those of the gaseous and condensed states. Interesting questions arise concerning how large a cluster must be before it will display bulk properties. Currently there is extensive research activity directed toward studies of their formation and varying properties and reactivity as a function of the degree of aggregation. Results serve to elucidate at the molecular level the course of change of a system to be followed from the gas to the condensed state, thereby enabling a spanning of the states of matter.     

The short-term temporal spectrum of precipitable water vapor

Short-term power spectra of the fluctuations in the precipitable water vapor measured with a dual-channel microwave radiometer are presented. The spectra, taken over 34-hour sampling periods, encompass periodicities from I day to about 10 minutes. The fluctuation power is associated with the average precipitable water vapor for the sampling period. The background noise spectrum of the radiometric instrument is also discussed.     

基于连续投影算法-遗传算法-BP神经网络的可见/近红外光谱木材识别

  目的  基于可见/近红外光谱技术,以10种木材为研究对象,探索不同预处理和特征提取方法下BP神经网络识别木材的效果。  方法  利用美国ASD公司生产的LabSpec 5000光谱仪采集10种木材的光谱图,分别进行移动平均法处理、移动平均法+多元散射校正(MSC)、移动平均法＋标准正态变量变换(SNV)、Savitzky-Golay卷积平滑算法(S-G滤波器)、S-G滤波器+MSC和S-G滤波器+SNV的预处理,运用主成分分析法(PCA)、连续投影算法(SPA)、SPA和遗传算法(GA)联合分别进行特征提取,将提取的特征结合BP神经网络进行木材识别试验。  结果  以SPA和GA联合提取光谱特征时,移动平均法+SNV的预处理效果最佳,以吸收峰为起始波段(W_initial=1 445 nm)、吸收峰个数为特征个数(N_tot=9)时,识别率较高,特征个数大部分减少为SPA提取特征值个数的一半左右。BP神经网络的平均识别速度提升明显。10种木材的平均识别率为98.0%,其中7种木材的识别率达到了100.0%。  结论  在移动平均法+SNV的预处理下,SPA和GA联合提取光谱图的特征,既可提高BP神经网络识别木材的正确率,又可提升识别速度。图3表6参23