标准氢与仲氢热力学性质的研究

本文首先对标准氢（Normalhydrogen）及仲氢（Parahydrogeh）的分子结构特性作了论述，然后对它们的热力学性质数据进行了分析研究和计算，并为工程计算提供了一套氢的物性基础数据。工程上广泛应用的是标准氢（25％的仲氢＋75％的正氢）。     

利用量子对应态原理预测正仲氢输运性质

基于量子对应态原理并考虑氢同分异构体之间的结构差异,建立了适用于预测低温正氢与仲氢输运参数的数学模型,明确了对比黏度和对比导热系数与对比德布罗意波长之间的线性关系,并使用所建立数学模型预测了正氢与仲氢的黏度与导热系数。通过对计算结果的检验分析,发现量子对应态原理方法可以较准确地预测温度20¹00 K及压力0.01¹0 MPa范围内正氢、仲氢的黏度及导热系数。压力对模型的预测精度影响显著,当环境压力小于1 MPa时,对应态原理预测误差基本控制在6%以内。进一步修正模型中的物性常数修正有望提高对应态原理预测精度。     

CSNS正仲氢转化及其组分测量的研究

本文分析了中子辐照环境下的仲氢向正氢转化的现象,结合CSNS低温系统的特点,开展了正仲氢转化反应器的方案设计,并在此基础上重点讨论了现有的正仲氢测量方案的特点.后续将根据项目现场的实际情况,开展正仲氢测量方案的选择和设计工作。正仲氢转化及其组分测量方案的研究,为后续CSNS低温系统的顺利建设提供理论基础。     

氢的转动配分函数及其热力学性质

当正氢和仲氢处于完全平衡态时,分子的转动配分函数为Z^rn=3/4Zo^r 1/4Zp^n;当氢气为正氢和仲氢的非平衡混合物时,分子的转动配分函数为Z湿^rn=(Zu^n)^N/N/o(Zp^r)^N/N/p,因实际的氢气在长时间内处于室温下的平衡态,当温度改变而成为非平衡混合物时,No/N≈3/4,Np/N≈`/4,因此,Z湿^rn=(Zo^r)^3/4(Zp^r)^1/4,由此求得的热容量与实验结果非常接近．     

Y1—xNdxSr2Cu2.7Mo0.3O7—δ体系的拉曼和红外光谱研究

利用拉曼散射和红外有收光谱研究了Ｙ１－ｘＮｄｘＳｒ２Ｃｕ．０ｍＯ０．３ｏ７－δ系列样品的声子振劝性质，实验结果表明，对ｘ＝０的样品，在拉曼光谱中主要出现２３２３，４４３，５２２和５７８ｃｍ＾－１几个特征峰，在中红外吸收光谱中出现５２２，５８０和６４６ｘｍ＾－１特征峰。     

维生素B12的激光共振拉曼光谱研究

本文用激光共振拉曼光谱研究了维生素Ｂ１２位于２７０－７８０ｃｍ＾－１的低频振动光谱。认为３４４，４７６和４８８ｃｍ＾－１拉曼峰分别是腺嘌呤，Ｃｏ－ＣＮ和Ｃｏ－ＣＨ３振动模。用实验证明了维生素Ｂ１２在５１４．５ｎｍ激光作用下发生部分光解，而且Ｃｏ－ＣＨ３比Ｃｏ－ＣＮ更容易断裂。测得了光照Ｂ１２后光解速曲线。     

锌原卟啉Ⅸ二甲酯及其轴向配合物的富里叶变换拉曼光谱和与其共…

本工作测定了锌原卟啉Ⅸ二甲酯及其２－，３－胺基吡淀，２－，３－甲基吡啶，咪唑和苯并咪唑的富里叶变换（ＦＴ）拉曼光谱，并将之与其共振拉曼光谱比较。轴向配体引起的卟啉环“心膨胀”效率是卟啉骨架模式的拉曼频率下降和电子吸收带红移的原因，吡啶取代基的位置及推电子性质等影响拉慢频率位移及电子吸收带红移的程度。     

钛酸铅镧Pb_(1-x)La_xTi_(1-x/4)O_3纳米晶的拉曼光谱研究

本文在２８８Ｋ和３７８Ｋ测定了不同Ｌａ含量Ｐｂ１－ｘＬａｘＴｉ１－ｘ／４Ｏ３纳米晶的拉曼光谱,同时在室温条件下测定了不同晶粒尺寸的Ｐｂ０．９Ｌａ０．１Ｔｉ０．９７５Ｏ３纳米晶的拉曼光谱,研究了Ｌａ含量和晶粒尺寸对各声子模频率的影响规律,讨论了影响峰形、峰位和峰宽的因素。     

现场时间分辨拉曼光谱研究不同pH值溶液中聚吡咯电极的氧化还…

对不同ｐＨ值溶液中聚吡咯的电化学氧化原行为进行了现场时间分辨拉曼光谱研究，结果表明，采用拉曼－循环伏安图可以克服充电电流给聚吡咯氧化还原峰电位的确定带来的困难。本文讨论了拉曼－循环伏安图中峰电位相对于常规循环伏安图中的氧化还原峰电位发生负移的原因。在酸性溶液中氧化还原时会出现与一定氧化程度的，质子化的聚吡咯链段有关的不稳定中间产物，这是常规拉曼光谱所不能获得的，体现了电化学现场的时间分辨拉曼光谱方     

Y_（1－x）Nd_xSr_2Cu_（2．7）Mo_（0．3）O_（7－δ）体系的拉曼和红外光谱研究

利用拉曼散射和红外吸收光谱研究了Ｙ１－ｘＮｄｘＳｒ２Ｃｕ２．７Ｍｏ０．３Ｏ７－δ（ｘ＝０，０．２，０．５，０．８，１．０）系列样品的声子振动性质。实验结果表明，对ｘ＝０的样品，在拉曼光谱中主要出现３２３，４４３，５２２和５７８ｃｍ－１几个特征峰，在中红外吸收光谱中出现５２２，５８０和６４６ｃｍ－１特征峰。随着样品中Ｎｄ组分的增加，３２３ｃｍ－１峰向低波数发生位移，而５２２和６４６ｃｍ－１峰则向高波数发生位移。本文对这些振动模进行了指认，并对其随不同样品组分的变化行为进行了讨论     

Raman gain measurement in solid parahydrogen

We report a steady-state Raman gain measurement of the Q(1)(0) transition (v = 1 ? 0, J = 0 ? 0) in solid parahydrogen. We carry out measurements by pumping with a continuous-wave frequency-doubled YAG laser at 532 nm and observing the direct amplification of a probe-laser beam for the first Stokes transition at 683 nm. A large single-pass amplification coefficient of 2.3 +/- 0.2 is obtained at a pump intensity of 46 kW/cm(2), with an interaction length of 1 cm, giving a steady-state Raman gain coefficient of 18 +/- 3 cm/MW.     

Structure of small hydrogen nanoclusters containing ortho-molecules

Using the quantum mechanical path integral Monte Carlo method, we simulated parahydrogen clusters (j = 0) and clusters doped with several (up to 6) orthohydrogen molecules (j = 1), with the total number of molecules ranging from 4 to 40 at temperatures of 1.5, 3, and 4.5 K. Some energy parameters (including the chemical potentials) and spatial characteristics of the clusters are found. At a temperature of 1.5 K, as the total number N of molecules in the cluster increases, the chemical potential and the rotational energy of the clusters attain local minima at the same geometrically determined values of N (the magic numbers). The ortho-molecules exhibit a larger probability (compared to the para-molecules) to reside in the central region of the cluster and a smaller probability to be located near its surface. This effect is enhanced as the number of orthohydrogen molecules in the cluster increases, the total number N of molecules grows, or the temperature is lowered.     

Temperature Dependence for the Relative Raman Cross Section of the Ammonia/Water Complex

The Raman spectra of aqueous ammonia solutions have been obtained between -40 and 25 degrees C. The Raman spectrum of neat water was also obtained at 25 degrees C and is characterized by two broad peaks observed at 3200 and 3400 cm(-1). The spectrum due to water is subtracted to determine the NH(3) spectrum at all temperatures. In ammonia-water solutions, the spectrum shows three features at measured displacements of 3250, 3316, and 3400 cm(-1). The feature at 3316 cm(-1) is assigned to the Q branch of the symmetric stretch. The broad, weak features at 3250 and 3400 cm(-1), previously assigned to rotational bands, are assigned to combination bands. The NH(3) combination bands are assigned by comparing with sum frequency generation (SFG) experiments, monitoring changes with temperature, and analyzing the polarization data. The rotational structure of the Q band is also discussed. As the temperature is lowered from 25 to -40 degrees C, an increase in the Raman intensity is observed for all bands. The relative Raman scattering cross section is determined from the numerically integrated area of the NH(3) Q branch at each temperature. Copyright 2001 Academic Press.     

利用光学-光学双共振研究谱线的碰撞增宽

利用光学-光学双共振光谱技术研究了NaK分子21Σ＋→６1Σ＋跃迁线的碰撞增宽。一台单模半导体激光器实现11Σ＋(v″,J″)→21Σ＋(v′,J′)的跃迁,另一单模半导体激光器激发21Σ＋(v′,J′)能级到６1Σ＋的振转能级,二激光束反向平行通过样品池。谱线总线宽与K原子密度成线性关系,由其斜率得到增宽速率系数k_br＝(1.4±0.7)×10-8 cm3·s-1。同时研究了21Σ＋(v＝8,J＝12)→21Σ＋(v＝8,J＝13,14)转动能级间的碰撞激发转移,测量谱线的相对强度,由速率方程得到碰撞转移速率分别为6.1×106和5.2×106 s-1。     

激发态H2(X1∑+g,v=1,J=1)之间的碰撞能量合并

受激拉曼激发H2(0,1)基态的Q支得到H2(1,1)能级.在室温条件下,利用反斯托克斯拉曼散射(CARS)探测技术测量了碰撞能量合并(EP)过程H2(1,1)+H2(1,1)→H2(2,J)+H2(0,J″)及H2(1,1)与H2(1,J)转动能级间的碰撞转移速率系数.扫描CARS谱表明在H2(1,1)能级的碰撞能量...     

Sub-Doppler Infrared Spectra of the OH-Stretch Fundamental of (13)C-Methanol

High-resolution infrared spectra of the (13)C-methanol OH stretching band, nu(1), were obtained by slit-jet absorption spectroscopy at a rotational temperature of 12-15 K. Twenty-eight subbands were assigned within the range of upper state quantum numbers, K' = 0 to 2 and J' = 0 to 10. The upper state energy levels are heavily perturbed; about half of the assigned subbands were found to be split by perturbations with matrix elements in the range 1-3 cm(-1). The doubled lines were deperturbed and together with the "unperturbed" lines were fitted to a global torsion-rotation Hamiltonian with root-mean-square deviation of 0.41 cm(-1) to yield a torsional barrier height of approximately 405 cm(-1) in the vibrationally excited state. Copyright 2000 Academic Press.     

The nu(1) and nu(3) Bands of the (17)O(16)O(17)O Isotopomer of Ozone

Using 0.002 cm(-1) resolution Fourier transform absorption spectra of an (17)O-enriched ozone sample, an extensive analysis of the nu(3) band together with a partial identification of the nu(1) band of the (17)O(16)O(17)O isotopomer of ozone has been performed for the first time. As for other C(2v)-type ozone isotopomers [J.-M. Flaud and R. Bacis, Spectrochim. Acta, Part A 54, 3-16 (1998)], the (001) rotational levels are involved in a Coriolis-type resonance with the levels of the (100) vibrational state. The experimental rotational levels of the (001) and (100) vibrational states have been satisfactorily reproduced using a Hamiltonian matrix which takes into account the observed rovibrational resonances. In this way precise vibrational energies and rotational and coupling constants were deduced and the following band centers nu(0)(nu(3)) = 1030.0946 cm(-1) and nu(0)(nu(1)) = 1086.7490 cm(-1) were obtained for the nu(3) and nu(1) bands, respectively. Copyright 2000 Academic Press.     

Raman scattering study of delafossite magnetoelectric multiferroic compounds: CuFeO2 and CuCrO2

Ultrasonic velocity measurements on the magnetoelectric multiferroic compound CuFeO(2) reveal that the antiferromagnetic transition observed at T(N1) = 14 K might be induced by an R3m --> pseudoproper ferroelastic transition. In that case, the group theory states that the order parameter associated with the structural transition must belong to a two-dimensional irreducible representation E(g) (x(2) - y(2), xy). Since this type of transition can be driven by a Raman E(g) mode, we performed Raman scattering measurements on CuFeO(2) between 5 and 290 K. Considering that the isostructural multiferroic compound CuCrO(2) might show similar structural deformations at the antiferromagnetic transition T(N1) = 24.3 K, Raman measurements have also been performed for comparison. At ambient temperature, the Raman modes in CuFeO(2) are observed at ω(E(g)) = 352 cm(-1) and ω(A(1g)) = 692 cm(-1), while these modes are detected at ω(E(g)) = 457 cm(-1) and ω(A(1g)) = 709 cm(-1) in CuCrO(2). The analysis of the temperature dependence of the modes in both compounds shows that the frequencies of all modes increase with decreasing temperature. This typical behavior is attributed to anharmonic phonon-phonon interactions. These results clearly indicate that none of the Raman active modes observed in CuFeO(2) and CuCrO(2) drive the pseudoproper ferroelastic transitions observed at the Néel temperature T(N1). Finally, a broad band at about 550 cm(-1) observed in the magnetoelectric phase of CuCrO(2) below T(N2) could be associated with magnons.     

LOCAL MODE SPECTROSCOPIC STUDY OF THE AsH3 MOLECULE: THE PERTURBED (500) LOCAL MODE OVERTONE

The high resolution Fourier transform spectra of AsH₃ in the region of 9720-9900 cm^-1, which had been recorded at a resolution of 0.015 cm^-1, were assigned to the (500; A₁) and (500; E) local mode overtones and rotationally analyzed. The effective spectroscopic parameters were obtained by nonlinear least-squares fitting the vibration-rotational Hamiltonian with the rotational energy levels up to J=6 (98 levels in all) included. The evolution of the rotational energy patterns from v=1 to v=6 shows that the tendency of normal mode to local mode vibration evolution has been stopped by perturbations in relatively high energy region.     

Rb(5PJ)与He,N2的碰撞精细结构混合和猝灭

在气体样品池条件下,研究了Rb(5PJ) (He,N2)碰撞能量转移过程.用调频半导体激光器激发Rb原子至Rb(5P3/2)态,在不同的He或N2气压下,测量了直接5P3/2→5S1/2荧光和转移5P1/2→5S1/2荧光.对于Rb(5PJ)与He的碰撞,只发生精细结构转移(略去碰撞猝灭效应),电子态能量仅能转移为He原子的平动能.在与N2的碰撞中,向分子振转态的转移是重要的.本实验中,Rb的密度为4.5×1011 cm-3,由辐射陷获理论得到5P1/2→5S1/2的有效辐射率为2.47×107 s-1.利用速率方程分析,可以得到碰撞转移速率系数,对于He,5P3/2→5S1/2转移速率系数kHe21=2.61×10 12 cm3·s.对于N2,测量5PJ He和5PJ N2两种情况下直接荧光与敏化荧光的相对强度比,利用最小二乘法确定5Pa/2→5S1/2转移速率系数kN212=2.36×10-11 cm3·s,5PJ态猝灭速率系数kN2=1.44×10-11 cm3·s-1.由实验结果证实了Cs-N2主要是直线式碰撞传能机制,与其他实验结果进行了比较.