Raman紫外双共振研究C2H2分子的碰撞转动弛豫

本文利用受激Raman抽运,选择性地制备了C₂H₂分子电子基态的红外非激活振动能级的单一转动态(X¹∑_g⁺,v″₂=1,J″=9,11,13),并从紫外激光诱导的A¹Au(v′₃=1)←X¹∑_g⁺(v″₂=1)荧光谱,直接测定上述三个转动态的C< 关键词：     

非晶锂离子导体B2O3-Li2O-LiCl一Al2O3中VO2+的电子自旋共振

两种非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃-0.1V₂O₅(x=0.05和0.15)的电子自旋共振谱研究表明:(i)ESR线型是高斯型,证实V₂O₅添加量适当;(ii)超精细结构来源于VO²⁺络离子,具有四角对称性,属C_4v群。越精细耦合张量的平行分量平均值A_//=0.0175cm^-1,垂直分量A_⊥=0.0063cm^-1。由g_//(g_⊥)求出其基态²B_2g与第一激发态²E_g的能级间距△₁=2.46×10⁴ cm^-1,基态与第二激发态²B_1g的能级间距△₂=3.03×10⁴ cm^-1;(iii)变温实验证实:Al₂O₃组分较少(x=0.05)的非晶ESR强度比x=0.15的非晶高3倍至2倍,而Al₂O₃组分越多则ESR强度随温升下降越小。     

332—362nm范围内CF2Cl自由基的共振增强多光子电离研究

用CF₂Cl₂分子直流脉冲放电的方法产生CF₂Cl自由基，结合共振增强多光子电离(REMPI)技术，测量了332—362nm波长范围内CF₂Cl自由基的(2+1)REMPI光谱，分析并标识了4s Rydberg态带源位于(ν_0—0=55371cm^-1)，两个被激活振动模ω′₃(CF₂剪式振动模)和ω₄′(OPL 关键词：     

密环菌甲素晶体结构研究

密环菌甲素(C₂₄H₃₀O₆)属正交晶系,空间群为P2₁ 2₁ 2₁,晶胞参数为a=18.784(9)?,b=14.002(7)?,c=8.598(5)?,z=4,计算密度D_c=1.216g·cm^-1。使用菲利浦PW-1100四圆衍射仪收集衍射强度。该结构是在MULTAN-78求解失败以后,使用MULTAN-80,在正切修正时选择统 关键词：     

BH2和AlH2分子的结构及其解析势能函数

运用二次组态相关(QCISD)方法，分别选用6-311++G(3df,3pd)和D95(3df,3pd)基组，对BH₂和AlH₂分子的结构进行了优化计算，得到BH₂分子的稳态结构为C_2v构型，电子态为²A₁、平衡核间距R_BH=0.1187nm、键角∠HBH=128.791°、离解能D_e=3.65eV、基态振动频率ν₁(a₁)=1020.103cm^-1,ν₂(a₁)=2598.144cm^-1,ν₃(b₂)=2759.304cm^-1.AlH₂分子的稳态结构也为C_2v构型，电子态为²A₁、平衡核间距R_AlH=0.1592nm、键角∠HAlH=118.095°、离解能D_e=2.27eV、基态振动频率ν₁(a₁)=780.81cm^-1,ν₂(a₁)=1880.81cm^-1，ν₃(b₂)=1910.46cm^-1.采用多体项展式理论推导了基态BH₂和AlH₂分子的解析势能函数，其等值势能图准确再现了BH₂和AlH₂分子的结构特征及其势阱深度与位置.分析讨论势能面的静态特征时得到BH+H→BH₂反应中存在鞍点，活化能为150.204kJ/mol；AlH+H→AlH₂反应中也存在鞍点，活化能为54.8064kJ/mol. 关键词： 2')" href="#">BH₂ 2')" href="#">AlH₂ Murrell-Sorbie函数 多体项展式理论 解析势能函数     

少量KCl引起水杨酸表面增强喇曼散射谱的异常变化

本文报道KCl引起的银胶中水杨酸(C₇H₄O₃)表面增强喇曼散射谱(SERS)的异常变化。发现KCl造成水杨酸分子中某些结构的SERS强度急剧而迅速下降,但同时又造成3436cm^-1附近v(—OH)振动的SERS信号的进一步增强。还研究了KCl对一系列含—COOH结构的分子(例如苯甲酸、对氨基苯甲酸等)SERS信号的影响,发现Cl^-对v(—COO^-)振动的SERS强度有明显的 关键词：     

NCO异构体结构与分析势能函数

在B3LYP/6-31+G（d）水平上,对NCO分子的各种可能结构进行几何优化,得到了NCO及其异构体分子CNO和CON基态结构都是C_∞v,电子态为X²Ⅱ,NCO分子的平衡核间距R_NC=0.1230 nm,R_CO=0.1186 nm,离解能D_e=13.40 eV,并计算出谐振频率ω₁=1293.44 cm^-1,ω₂（A′）=484.73 cm^-1,ω₂（A″）=559.72 cm^-1,ω₃=1988.41 cm^-1,Renner-Teller参数ε=-0.1429,计算值与实验值吻合较好.在此基础上,应用多体项展式理论,单体项中首次引入开关函数,三体项以NCO,CNO基态结构与性质为依据,拟合给出了NCO分子的基态分析势能函数,其等值势能图准确再现了NCO,CNO分子基态结构与特征,并与优化结果完全一致.     

CaO-Al2O3二元系晶体和玻璃的拉曼光谱研究

实验测定了CaO-Al₂O₃二元系中晶体和玻璃的拉曼光谱,并利用密度泛函理论(DFT)计算了CaAl₄O₇晶体的拉曼光谱活性振动波数和散射活性。结果表明CaAl₄O₇的中波数区(400～700 cm^-1)对应Al-O_b-Al的弯曲振动,高波数区(700～1 000 cm^-1)则对应Al-O_nb的伸缩振动。采用激光悬浮加热装置制备了一系列玻璃样品,对其进行拉曼光谱研究发现,550和780 cm^-1附近观察到两个明显的特征峰,分别对应Al-O_b-Al的弯曲振动和Al-O_nb的伸缩振动。随着CaO/Al₂O₃比例的增加,550 cm^-1特征峰发生蓝移,而780 cm^-1特征峰发生红移,表明复杂网络结构逐渐解聚。此外,随Al<...     

TWO PHOTONS EXCITED 4d RYDBERG STATE OF AsH3

In this paper, by using resonance enhanced (2+1) multiphoton ionization (REMPI) of AsH₃ and detecting the daughter molecular ions AsH⁺ and As⁺, a long progression discrete structure was obtained from 267 to 291 nm, which obeys the formula ν₀(cm^-1)=68875.3+504.1v′₂+5.26v′²₂. Analysis of the spectrum has revealed that it belongs to 4d Rydberg state transition. Our assignment yields the 4d Rydberg state parameters T_e′=67881.1 cm^-1, ω_e′=495.1 cm^-1 and δ=0.962. Finally the 4d Rydberg state structure of AsH₃ was discussed.     

超声射流冷却CCl2自由基的激光诱导荧光激发谱

在497—517nm波长范围观测超声射流冷却CCl₂自由基的激光诱导荧光激发谱。得到CCl₂在?←X跃迁中(v₁,v₂,0)←(0,0,0)振动带清晰的K结构。对近80个子谱带作了归属。振动分析给出较精确的v＇₁和v＇₂振动频率和非谐性常数;从K结构的分析得出(A＇-B＇)和(A″-B″)的值,文献未曾报道过。 关键词：     

The rotational spectra of the υ8 = υ9 = 1 and υ6 = υ7 = 1 interacting vibrational states of nitric acid (HNO3)

The analysis of the rotational spectrum of HNO₃ has been extended to include the υ₈ = υ₉ = 1 state at 1205.7 cm⁻¹ and the υ₆ = υ₇ = 1 state at 1223.4 cm⁻¹. Based on 78-519 GHz data, the assignments in the 8¹9¹ vibrational state have been significantly expanded from the previously reported microwave measurements [T.M. Goyette, F.C. De Lucia, J. Mol. Spectrosc. 139 (1990) 241-243]. A new microwave analysis is also reported for the 6¹7¹ vibrational state. A simultaneous analysis takes into account the localized ΔK_a = ±2 Fermi resonances between the vibrational states, describes the torsional splitting of 3.3 and 1.4 MHz for the 8¹9¹ and 6¹7¹ states respectively, and fits to experimental accuracy over 1500 rotational transition frequencies that extend up to J = 59. Infrared energy levels [A. Perrin, J.-M. Flaud, F. Keller, A. Goldman, R. D. Blatherwick, F. J. Murcray, C. P. Rinsland, J. Mol. Spectrosc. 194 (1999) 113-123] were also included in the analysis and fit to experimental accuracy. Measurement of strongly perturbed transitions in each vibrational state provide a determination of the band origin difference of 17.733184(17) cm⁻¹. The rotational constants agree well with those predicted by vibrational-rotational constants of the fundamental modes. Furthermore, the analysis will provide a very accurate simulation of the infrared spectrum of HNO₃ in the 8.3 μm region.     

The rotational spectra of the 79, 69, and 7 vibrational states of nitric acid

The rotational spectra of the first three vibrational states of nitric acid above 1000 cm⁻¹, 7¹9¹, 6¹9¹, and 7², have been measured and analyzed. The 7² state, along with the previously published 7¹ state, show the rotational and centrifugal distortional constants have a near linear dependence on the υ₇ vibrational quantum number. Large changes for several centrifugal distortion constants of the υ₇ = n series of states are attributed to a c-type Coriolis resonance manifold between the ν₇ and ν₆ vibrational modes and the Hamiltonian reduction and representation used to fit the spectra. The 7¹9¹ and 6¹9¹ states have torsional splittings of 12.361(8) and 22.47(1) MHz, respectively. These splittings are large compared to 2.340(8) MHz of the 9¹ state and can be explained by a ∼1-2% mixing through anharmonic Fermi resonances with the 9³ state, which has a large torsional splitting of ∼1760 MHz. The millimeter/submillimeter-wave spectrum of each state was fit separately to the experimental uncertainty of the measurements. The resultant rotational constants, distortional constants and inertial defects agree well with DFT calculations.     

Evolution of the homogeneous IR spectrum of a highly vibrationally excited molecule as a result of a change in its vibrational energy

Using a photodissociation technique, we have measured the IR spectrum of thev ₂₁ mode of the (CF₃)₃ CI molecule with a vibrational energy ofE ₂=42500±3500 cm^–1 which is more than two times the dissociation energy. The experimental spectrum of a Lorenzian shape with a halfwidth of ₂=10.8±1.5 cm^-1 has been analyzed simultaneously with the results of the preceding work (₁=8.6±0.6 cm^-1) that were obtained at a lower vibrational energy (E ₁=36500±2500 cm^–1).     

Rotational spectrum of trans-trans diethyl ether in the ground and three excited vibrational states

We report the results of a comprehensive reinvestigation of the rotational spectrum of diethyl ether based on broadband millimetre-wave spectra recently recorded at The Ohio State University and in Warsaw, covering the frequency region 108-366 GHz. The data set for the ground vibrational state of trans-trans diethyl ether has been extended to over 2000 lines and improved spectroscopic constants have been determined. Rotational spectra in the first excited vibrational states of the three lowest vibrational modes of trans-trans-diethyl ether, ν₂₀, ν₃₉, and ν₁₂ have been assigned. The v₂₀ = 1 and v₃₉ = 1 states are near 100 cm⁻¹ in vibrational term value and are coupled by a strong c-axis Coriolis interaction, which gives rise to many spectacular manifestations in the rotational spectrum. All of these effects have been successfully fitted for a dataset comprising over 3000 transitions, leading to precise determination of the energy difference between these states, (ΔE/hc)=10.400222(5) cm⁻¹. A newly developed software package for assignment and analysis of broadband spectra is described and made available.     

The vibration-rotation HDO absorption spectrum between 8558 and 8774 cm−1

The absorption spectrum of HDO has been recorded in the region 8558–8774 cm^?1 using a high-sensitivity intracavity F₂^?:LiF center laser spectrometer. The absorption sensitivity is 10^?7 cm^?1 and the line-center determination accuracy is about 4 × 10^?2 cm^?1. The spectrum was interpreted and the absorption lines were attributed to the ν₂ + 2ν₃ band of HDO. Energy levels up to J = 12 and rotational and centrifugal parameters of the vibrational (012) state were obtained.     

Carbon suboxide: The infrared spectrum from 1800 to 2600 cm−1

The infrared spectrum of carbon suboxide has been recorded from 1800 to 2600 cm^?1 at a resolution of 0.003 cm^?1. About 7% of the ca. 40 000 lines observed have been assigned and analyzed, belonging to 36 different bands. Most of these are associated with the fundamental ν₃, at 2289.80 cm^?1, and the combination band ν₂ + ν₄, at 2386.61 cm^?1, each of which give rise to a system of sum bands, difference bands, and hot bands involving the low-wave-number fundamental ν₇ at 18 cm^?1. A few other tentative assignments are made. The bands have been analyzed for vibrational and rotational constants.     

Higher ro-vibrational levels of H2O deduced from high resolution oxygen-hydrogen flame spectra between 6200 and 9100 cm-1

The spectra of hydrogen-oxygen and acetylene-oxygen flames have been recorded on a Fourier transform spectrometer in the region 6200–9100 cm^-1 with a resolution of 0·015 cm^-1. In this region, we have performed a detailed analysis of the 2v ₂ + v ₃, v ₁ + v ₃, v ₁ + v ₂ + v ₃ - v ₂ and v ₁ + v ₂ + v ₃ bands. A primary motive for this study was to obtain higher rotational energy levels for the (021), (101) and (111) vibrational states. Moreover an extensive set of rotational levels of the (010) vibrational state has been deduced from the combined study of hot bands involving the (011), (021) and (111) vibrational states. A room-temperature absorption spectrum of water recorded on a Fourier transform spectrometer in the region 1750–2300 cm^-1 (resolution 0·005 cm^-1) has also been used to confirm the analysis.     

Rotational spectrum and structure of asymmetric dinitrogen trioxide, N2O3

The rotational spectra of the ground vibrational state and the ν₉ = 1 torsional state have been reinvestigated and accurate spectroscopic constants have been determined. The torsional frequency, ν₉ = 70(15) cm⁻¹, has been determined by relative intensity measurements. The assignment of the infrared spectrum has been slightly revised and an accurate harmonic force field has been calculated. The equilibrium structure has been determined using different, complementary methods: experimental, semi-experimental and ab initio, leading to r(NN) = 1.870(2) Å, in particular.