Structure and rotational dynamics of methyl propionate studied by microwave spectroscopy

We report on the rotational spectra of the most abundant conformer of methyl propionate, CH₃CH₂COOCH₃, recorded with a Fourier transform microwave spectrometer under molecular beam conditions. We present accurate rotational constants and centrifugal distortion constants. For the propionyl CH₃ CH₂CO– methyl group and the methoxy –OCH₃ methyl group, barriers of 820.46(99)?cm^?1 and 429.324(23)?cm^?1, respectively, were found. For spectral analysis, two different computer programs were used, the code BELGI-C_s-2tops based on the rho axis method (RAM) and the code XIAM based on the combined axis method (CAM). The results are compared. The experimental work was supplemented by quantum chemical calculations. Potential energy functions for the rotation of the terminal methyl groups and also of the entire ethyl group were parametrized.     

In situ analysis of chiral components of pichtae essential oil by means of ROA spectroscopy: experimental and theoretical Raman and ROA spectra of bornyl acetate

In this paper, a novel approach to analyze in situ (−)‐bornyl acetate (BA) in pichtae essential oil (Siberian fir needle oil, Abies sibirica oil) by means of Raman optical activity (ROA) is reported. As part of this approach, a conformational study in the gas phase of (+)‐ and (−)‐BA has been carried out, predicting the presence of three conformers for each enantiomer at 298.15 K. The structures of these conformers were optimized with density functional theory with the Becke 3LYP functional and 6–311 + + g** basis set. Subsequently, the Raman and ROA spectra were simulated in order to compare them with the experimentally measured spectra of the neat enantiomers of BA. Finally, the combination of Raman and ROA spectroscopy as well as DFT calculations was successfully applied not only for the detection of BA but also for the determination of the specific enantiomer of BA present in the investigated pichtae essential oil samples. Thus, the ROA technique described here has the potential to be used as a fast and easy commercial method to control the quality of essential oils. Copyright © 2011 John Wiley & Sons, Ltd.     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy and ab initio calculations of N-methylformamide

Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH₃, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V₃, to CH₃ internal-rotation: 53.9 (6) and 301 (4) cm⁻¹ for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm⁻¹ for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with ¹³C, ¹⁵N, or ¹⁸O singly-substituted in the internal-rotation A state were observed and analyzed to derive the r_s structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH₃ internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH₃ internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH₃ internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V₆ term is briefly discussed.     

载流子复合对时间分辨法拉第旋转光谱的影响

利用二能级体系速率方程,推导了半导体中探测光探测到的法拉第旋转光谱的理论模型,发现电子-空穴对的复合对法拉第旋转信号随时间的衰减有重要影响,并利用该模型对GaAs量子阱中实验测得的法拉第旋转光谱进行拟合,得到GaAs量子阱材料中的电子自旋弛豫时间为73.5 ps,而直接利用单指数进行拟合得到的电子自旋弛豫时间仅为51.3 ps. 因此,直接利用单指数对法拉第旋转光谱进行拟合得到电子自旋弛豫时间的传统做法是不准确的. 关键词： 自旋弛豫时间 时间分辨法拉第旋转光谱 GaAs量子阱     

Fourier transform microwave spectroscopy of 1,1-dimethylsilacyclobutane. Interplay of two types of large-amplitude motions: two-top internal rotation and ring puckering

1,1-Dimethylsilacyclobutane, abbreviated as DMSCB, was investigated by Fourier transform microwave spectroscopy, by paying special attention to two types of large-amplitude motions in the molecule: two-top internal rotation and four-membered ring puckering and also to the coupling between the two. In order to clarify the unique feature of the internal dynamics in DMSCB in detail, two independent approaches were employed, one being a combination of a standard two-top theory of internal rotation and an established theory of ring puckering and the other a theory of large-amplitude motions developed by Hougen and his collaborators. In accordance with predictions by the two approaches based on symmetry consideration, the observed rotational spectra were found split into eight (or six when AE/EA lines were not resolved) components, which were assigned to the two-top states of AA, AE, EA, and EE symmetry, each being further split by puckering into two: the symmetric and antisymmetric states. The analyses by two approaches gave spectroscopic results, which were in good agreement with each other. The spectroscopic data on the normal species, combined with those on Si and C isotopic species, yielded molecular structure parameters including the puckering angle (the dihedral angle between the CSiC and CCC planes) of 28.64° or 30.26° (two possible sets). The splitting between the two lowest puckering states was determined to be 11.90(22) MHz, which led, with the equilibrium puckering angle, to the potential barrier to puckering of 395.3 or 347.0 cm⁻¹ for the two sets, respectively, which was slightly lower than the value 440 cm⁻¹ in a “parent” molecule: silacylcobutane. The first-order terms of the coupling between CH₃ internal rotation and overall rotation were converted to the barrier to internal rotation of 567.8 and 505.1 cm⁻¹ in the AE (two methyl groups rotating in the same direction, as viewed from Si) and EA (two methyl groups rotating in the opposite direction) states, respectively, which corresponded to the torsional frequencies of 154 and 144 cm⁻¹, at variance with the Raman data of 177 and 172 cm⁻¹, previously reported in literature.     

Fourier transform microwave spectroscopy of N,N-dimethylacetamide

The jet-cooled Fourier-transform microwave spectrum of N,N-dimethylacetamide was recorded in the region of 12-24 GHz, and was analyzed to determine rotational constants and nuclear quadrupole coupling constants. Coriolis-like coupling parameters characterizing interaction between internal rotation of methyl groups and the overall rotation were also determined from internal-rotation tunneling splittings of the rotational transitions. The Coriolis-like coupling parameters permitted determination of the barrier heights to internal rotation of the three methyl groups, which were found to be 677, 237, and 183 cm⁻¹ for the C-methyl top, the trans-N-methyl top and the cis-N-methyl top, respectively.     

The geometry of organophosphonates: Fourier-transform microwave spectroscopy and ab initio study of diethyl methylphosphonate, diethyl ethylphosphonate, and diisopropyl methylphosphonate

The rotational spectra of diethyl methylphosphonate (DEMP), diethyl ethylphosphonate (DEEP), and diisopropyl methylphosphonate (DIMP) in supersonic expansions have been acquired using Fourier-transform microwave spectroscopy. Spectroscopic constants have been determined for five distinct conformers of the three molecules. Experimental data have been compared to ab initio calculations performed for each species. For both DEMP and DEEP, the calculations indicate the presence of several low-energy conformers (i.e., ?∼400 cm⁻¹ above the ground state) may be present at room temperature (300 K) for both DEMP and DEEP. When entrained in a supersonic expansion, the rotational temperatures of the samples are much colder (∼2 K); nonetheless, spectra from three conformers of DEEP are still observed experimentally, whereas only one conformer of DEMP is observed. In contrast, only a single low-energy conformer of DIMP is predicted by theory, and is present in the molecular beam. The relative abundance of low-energy conformers of DEMP and DEEP is attributed to the flexibility of the ethoxy groups within each molecule. The presence of multiple DEEP conformers in the supersonic beam indicates a more complex potential energy surface for this molecule that is directly related to conformational shifts of the PCH₂CH₃ group. Conversely, the absence of low-energy conformers of DIMP is attributed to steric hindrance between isopropoxy groups in the molecule. The internal rotation barrier for the PCH₃ group in DEMP and DIMP is compared to that found in DMMP and several phosphonate-based chemical weapon agents.     

Internal rotation and chlorine nuclear quadrupole coupling of o-chlorotoluene studied by microwave spectroscopy and ab initio calculations

The microwave spectrum of o-chlorotoluene has been reinvestigated using molecular beam Fourier transform microwave (MB-FTMW) spectrometers in the frequency range of 4–23 GHz. Due to the high resolution of this molecular beam technique the analysis yielded improved rotational constants, centrifugal distortion constants, and, for the first time, the complete chlorine nuclear quadrupole coupling tensor. From the torsional fine structure the barrier to internal rotation of the methyl group was found to be 5.5798(52) kJ mol⁻¹. Experimental results and ab initio calculations are compared.     

Effects of the structural order of canthaxanthin on the Raman scattering cross section in various solvents: A study by Raman spectroscopy and ab initio calculation

In this work,we measure the Raman scattering cross sections(RSCSs) of the carbon-carbon(CC) stretching vibrational modes of canthaxanthin in benzene,acetone,n-heptane,cyclohexane,and m-xylene.It is found that the absolute RSCS of CC stretching mode of canthaxanthin reaches a value of 10 24 cm 2 ·molecule 1 ·sr 1 at 8×10 5 M,which is 6 orders of magnitude larger than general RSCS(10 30 cm 2 ·molecule 1 ·sr 1),and the RSCSs of canthaxanthin in various solvents are very different due to the hydrogen bond.A theoretical interpretation of the magnetic experimental results is given,which is introduced in a qualitative nonlinear model of coherent weakly damped electron-lattice vibration in the structural order of polyene chains.In addition,the optimal structure and the bond length alternation(BLA) parameter of canthaxanthin are calculated using quantum chemistry calculation(at the b3lyp/6-31g(d,p) level of theory).The theoretical calculations are in good agreement with the experimental results.Furthermore,the combination of Raman spectroscopy and the quantum chemistry calculation study would be a quite suitable method of studying the structures and the properties of the π-conjugated systems.     

Quantitative detection of adulterated olive oil by Raman spectroscopy and chemometrics

Commercially available extra virgin olive oils are often adulterated with some other cheaper edible oils with similar chemical compositions. A set of extra virgin olive oil samples adulterated with soybean oil, corn oil and sunflower seed oil were characterized by Raman spectra in the region 1000–1800 cm⁻¹. Based on the intensity of the Raman spectra with vibrational bands normalized by the band at 1441 cm⁻¹ (CH₂), external standard method (ESM) was employed for the quantitative analysis, which was compared with the results achieved by support vector machine (SVM) methods. By plotting the adulterant content of extra virgin olive oil versus its corresponding band intensity in the Raman spectrum at 1265 cm⁻¹, the calibration curve was obtained. Coefficient of determination (R²) of each curve was 0.9956, 0.9915 and 0.9905 for extra virgin olive oil samples adulterated with soybean oil, corn oil and sunflower seed oil, respectively. The mean absolute relative errors were calculated as 7.41, 7.78 and 9.45%, respectively, with ESM, while they were 5.10, 6.96 and 4.55, in the SVM model, respectively. The prediction accuracy shows that the ESM based on Raman spectroscopy is a promising technique for the authentication of extra virgin olive oil. The method also has the advantages of simplicity, time savings and non‐requirement of sample preprocessing; especially, a portable Raman system is suitable for on‐site testing and quality control in field applications. Copyright © 2011 John Wiley & Sons, Ltd.     

基于7.6μm量子级联激光的光声光谱探测N_2O气体

近年来,气候变化对地球的生态环境产生严重影响,而大气温室气体在气候变化中具有重要的作用.一氧化二氮(N_2O)作为一种重要的温室气体,其浓度变化对大气环境产生重要影响,因此对其浓度的探测在大气环境研究中具有重要意义.本文开展了基于中国自主研发的7.6μm中红外量子级联激光的共振型光声光谱探测N_2O的研究,建立了N_2O光声光谱传感实验系统.此系统在传统的光声光谱探测的基础上优化改进,采用双光束增强的方式,增加了有效光功率,进一步提高了系统的探测灵敏度.探测系统以1307.66 cm~(-1)处的N_2O吸收谱线作为探测对象,结合波长调制技术对N_2O气体进行探测研究.通过对一定浓度的N_2O气体在不同调制频率和调制振幅的光声信号的探测,确定了系统的最佳调制频率和调制振幅分别为800 Hz和90 mV.在最优实验条件下对不同浓度的N_2O气体进行了测量,获得了系统的信号浓度定标曲线.实验表明,在锁相积分时间为30 ms时,系统的浓度探测极限为150×10~(-9).通过100次平均后,系统噪声进一步降低,实现了大气N_2O的探测,浓度探测极限达到了37×10~(-9).     

Formation and dissociation of protonated cytosine–cytosine base pairs in i-motifs by ab initio quantum chemical calculations

Formation and dissociation mechanisms of C-C＋ base pairs in acidic and alkaline environments are investigated, employing ab initio quantum chemical calculations. Our calculations suggest that, in an acidic environment, a cytosine monomer is first protonated and then dimerized with an unprotonated cytosine monomer to form a C-C＋ base pair; in an alkaline environment, a protonated cytosine dimer is first unprotonated and then dissociated into two cytosine monomers. In addition, the force for detaching a C-C＋ base pair was found to be inversely proportional to the distance between the two cytosine monomers. These results provide a microscopic mechanism to qualitatively explain the experimentally observed reversible formation and dissociation of i-motifs.     

Numerical investigation on photonic microwave generation by a sole excited-state emitting quantum dot laser with optical injection and optical feedback

Based on three-level exciton model, the enhanced photonic microwave signal generation by using a sole excited-state(ES) emitting quantum dot(QD) laser under both optical injection and optical feedback is numerically studied. Within the range of period-one(P1) dynamics caused by the optical injection, the variations of microwave frequency and microwave intensity with the parameters of frequency detuning and injection strength are demonstrated. It is found that the microwave frequency can be continuously tuned by adjusting the injection parameters, and the microwave intensity can be enhanced by changing the injection strength. Moreover, considering that the generated microwave has a wide linewidth, an optical feedback loop is further employed to compress the linewidth, and the effect of feedback parameters on the linewidth is investigated. It is found that with the increase of feedback strength or delay time, the linewidth is evidently decreased due to the locking effect. However, for the relatively large feedback strength or delay time, the linewidth compression effect becomes worse due to the gradually destroyed P1 dynamics. Besides, through optimizing the feedback parameters, the linewidth can be reduced by up to more than one order of magnitude for different microwave frequencies.     

Resonance Raman spectroscopy and theoretical study on the photodissociation dynamics of diuron in S2 state

Resonance Raman spectra (RRs) and quantum chemical calculations were used to investigate the photodissociation dynamics of diuron in S₂ state. The RRs indicate that the photorelaxation dynamics for the S₀ → S₂ excited state is predominantly along nine motions: the ring C = C stretch vibration ν₁₂ (1593 cm⁻¹), Ph–N–H wag ν₁₄ (1517 cm⁻¹), CO–N(CH₃)₂ stretch ν₂₃ (1365 cm⁻¹)_, CCH wag in plane/ring C = C stretch ν₂₄ (1297 cm⁻¹)_, ring CH rock in plane/ring deformation ν₂₇ (1233 cm⁻¹), CCH wag in plane ν₂₉ (1151 cm⁻¹), Ph–Cl (para) stretch ν₃₅ (1028 cm⁻¹), Ph–N–H wag ν₃₇ (913 cm⁻¹) and ring breath ν₄₄ (685 cm⁻¹). Dissociation by Ph–Cl (para) cleavage at S₂ state directly or relaxation to T₂ state by internal conversion (S₂ → S₁) and intersystem crossing (S₁/T₂) is expected by ~250 nm irradiation based on the RRS, complete active space self‐consistent field, configuration interaction singles and time‐dependent density functional theory calculations. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural analysis of xCsCl(1−x)Ga2S3 glasses by means of DFT calculations and Raman spectroscopy

The alkali metal halide doping of gallium‐sulfide glasses yields improvements in the optical, thermal and glass forming properties. To understand these improvements, the short‐range order of xCsCl(1 − x)Ga₂S₃ glasses was probed by Raman spectroscopy. Raman spectra have been interpreted using density functional theory (DFT) harmonic frequency calculations on specific clusters of GaS₄H₄ and/or GaS₃H₃Cl tetrahedral subunits. The assignment of the observed vibrational bands confirms the main structural conclusions obtained with X‐ray and neutron diffraction experiments and gives some new insights into the gallium‐network present in the xCsCl(1 − x)Ga₂S₃ glasses. At the lowest concentration, the observed spectrum may be interpreted with small clusters such as dimers and trimers connected by corner‐sharing (CS) GaS₄H₄ tetrahedral subunits. The vibrational fingerprints of tri‐clusters with three‐fold coordinated sulfur atoms have also been identified; however, no Raman signature of chlorine‐doped subunits has been found to be caused by their insufficient intensity. For higher CsCl concentrations, distinct spectral features corresponding to chlorine‐doped clusters appear and are increasing in intensity with x. In other words, undoped and Cl‐doped tetrahedra coexist in the xCsCl(1 − x)Ga₂S₃ glasses. The added chlorine atoms induce a fragmentation of the glass network and replace the sulfur atoms in the CS tetrahedral environment. The comparison of the observed spectra with theoretical predictions and diffraction data favoured one‐fold coordinated chlorine atoms in the glass network. Copyright © 2009 John Wiley & Sons, Ltd.     

基于中红外量子级联激光器和石英增强光声光谱的CO超高灵敏度检测研究

采用石英增强光声光谱(QEPAS)技术对CO痕量气体展开检测研究. 为了实现超高灵敏度探测, 采用输出波长为4.6 μm的新颖中红外高功率分布反馈量子级联激光器为光源, 实现了对CO气体基频吸收带的激发与测量. 在优化了调制深度、气体压强和提高了CO分子的振动-转动弛豫速率后, 获得了1.95 ppbv的优异探测极限. 在分析检测结果的过程中, 讨论了能级寿命对信号强度的影响, 并对QEPAS信号强度的表达式进行了修正.     

本征GaAs量子阱中电子自旋扩散输运的时-空分辨吸收光谱研究

发展了一种时-空分辨圆偏振光抽运-探测光谱及其理论,并用于本征GaAs量子阱中电子自旋扩散输运的实验研究.获得室温下本征GaAs量子阱中的“自旋双极扩散系数”为D_as=37.5±15 cm²/s.此结果比用自旋光栅法测量到的掺杂GaAs量子阱中电子自旋扩散系数小.解释为是由于“空穴库仑拖曳”效应减慢了电子自旋波包的扩散输运. 关键词： 时-空分辨抽运-探测光谱 电子自旋扩散 GaAs量子阱     

Vibrational spectra,X‐ray and molecular structure of 1H‐ and 3H‐imidazo[4,5‐b]pyridine and their methyl derivatives: DFT quantum chemical calculations

Molecular structure, vibrational energy levels and potential energy distribution of 1H‐imidazo[4,5‐b]pyridine, 3H‐imidazo[4,5‐b]pyridine, 5‐methyl‐1H‐imidazo[4,5‐b]pyridine, 6‐methyl‐1H‐imidazo[4,5‐b]pyridine and 7‐methyl‐3H‐imidazo[4,5‐b]pyridine were determined using density functional theory (DFT) at the B3LYP/6‐31G(d,p) level. The optimised bond lengths and bond angles are in good agreement with the X‐ray data of 5‐methyl‐1H‐imidazo[4,5‐b]pyridine obtained in the present work (Pbca space group; a = 8.660(2), b = 11.078(2), c = 11.078(3) Å, Z = 8). The N⁺H group plays the role of a proton donor in a medium strong hydrogen bond of the type N H…N, linking the N‐atom of the pyridine with the adjacent molecule related by the symmetry operation: 1/2 − x, y − 1/2, z(N…N = 2.869(25) Å). The presence of hydrogen bond is confirmed by appearance in the IR spectra of a very broad and strong contour in the 2000–3100 cm⁻¹ range. The place of substitution of the methyl group at the pyridine ring influences the proton position of the NH group at the imidazole unit. Copyright © 2007 John Wiley & Sons, Ltd.     

Fourier transform microwave spectroscopy of LiCCH, NaCCH, and KCCH: Quadrupole hyperfine interactions in alkali monoacetylides

The alkali metal monoacetylides LiCCH, NaCCH, and KCCH and their deuterium isotopologues have been investigated using Fourier transform microwave (FTMW) spectroscopy in the frequency range 5-37 GHz. The molecules were synthesized in a supersonic expansion by the reaction of metal vapor, produced by laser ablation, with acetylene or DCCD. Use of target rods of the pure metal and a DC discharge immediately following the laser interaction region were significant factors in molecule production. Multiple rotational transitions were recorded for all species, except where only the J = 1 → 0 line was accessible (Li species). Quadrupole hyperfine interactions arising from the metal nuclei were resolved in each molecule, as well as those from the deuterium nucleus in the deuterated isotopologues. From a combined analysis with previous millimeter-wave data, refined rotational constants were determined for these species, as well as ⁷Li, ²³Na, ³⁹K, and D eQq parameters. The values of the metal quadrupole coupling constants are comparable to those of the alkali halides and hydroxides, indicating a similar degree of ionic character in the metal-ligand bond.