费米共振对分子振动能级和光谱的影响

费米共振相互作用对多原子分子具有相同对称类的近简并振动能级及其光谱产生影响,利用定态微扰理论,分析了五阶近似下费米共振对三个振动能级的影响,应用于CO2分子的(0400),(1200)和(2000)三个近简并能级,计算结果与实验观测值符合较好,并讨论了费米共振对(0400),(1200)和(2000)向(0110)能级跃迁时光谱线强度的影响.     

~6Li超冷费米气体窄Feshbach共振的实验研究

我们通过精确锁定Feshbach共振线圈中的电流,获得了稳定度接近10-5的Feshbach共振磁场。利用RF射频谱和原子共振损失谱精确地测量了超冷6 Li费米原子气体的窄Feshbach共振,研究了该Feshbach共振的相互作用和原子气体的能量依靠关系,测量了原子内态相互作用和密度所导致的射频跃迁的散射碰撞频移。这种能量依靠的相互作用的费米原子气体具有重要的意义,可以产生新奇的超流,用来模拟中子星物质的态方程。     

用CS2分子研究振动局域态的纠缠和能量

研究CS₂费米共振耦合振动局域态的Neumann纠缠熵动力学, 并研究伸缩与弯曲振动的相互作用能量, 目的是建立纠缠与能量的联系. 结果表明伸缩振动局域态的纠缠与能量是反关联更明显, 而弯曲振动局域态的纠缠与能量是正关联更明显. 还讨论了非局域态的纠缠与能量的关系.     

TiO_2缺陷结构电子性质的第一性原理计算

本文采用第一性原理研究了O空位缺陷、Ti空位缺陷TiO_2的能带结构、总态密度、吸收谱.通过研究发现:与TiO_2超胞结构的能带相比,O空位缺陷体系的价带与导带能量均向低能区域移动,费米能级与导带底交错,呈现出n型半导体,Ti空位缺陷的TiO_2的费米能级与价带顶部的能级交错,为p型半导体材料.对于O空位缺陷TiO_2总态密度与分波态密度在低能区的态密度则主要由O的3s、3p轨道贡献的能量,而在费米能附近的态密度则主要由Ti的4d轨道贡献能量;Ti空位缺陷的态密度总态密度仍然由O的3s、3p和Ti的4d轨道贡献的能量;同时分析吸收光谱发现峰值下移较多的是钛缺陷体系,其原因在于Ti缺陷结构中未成键电子的相互作用.     

四氯化碳费米共振的拉曼光谱研究

费米共振现象是一种广泛存在于分子振动光谱中的现象,特别是结构比较复杂的多原子分子.在多原子分子中当振动倍频或组合频位于某一基频附近,由于发生振动耦合,会出现两个新峰,峰的位置向两侧发生移动,二者谱线强度发生变化,把这种现象称为费米共振.费米共振现象不仅存在于红外光谱中,也存在于拉曼光谱中.文章中测量了CCl4的拉曼光谱,利用所得到的谱线峰位和用Originpro7.5软件程序获得积分强度,用费米共振的相关理论计算了C-Cl的a1对称伸缩振动频率v1与C-Cl2的f对称弯曲振动频率v4的组合频(v1 v4)与(某一未知基频)C-Cl的f对称伸缩振动频率v03的费米共振特征参数,进而计算出了耦合系数W和这一未知基频v03.该文对理解费米共振,了解分子振动频率,研究分子结构有很重要的参考价值.     

耦合Majorana束缚态T形双量子点中的Andreev反射

研究了连接在正常金属电极和超导电极之间的耦合Majorana束缚态(MBSs)T形双量子点结构中的Andreev反射.研究发现,对于T形双量子点结构,当入射能量等于边耦合量子点能级时Andreev反射电导出现Fano振荡,连接MBSs之后,零费米能附近出现一对新的Fano型振荡峰.如果忽略两个MBSs之间的相互作用,零费米能点的Andreev反射电导为定值1/2G_0(G_0=2e~2/h),不受量子点能级、双量子点之间耦合强度以及量子点与MBSs之间的耦合强度的影响.此外,在没有耦合MBSs的T形双量子点结构中,调节双量子点间的耦合强度可以使零费米能附近的Andreev反射电导出现由共振带向反共振带的转变,而耦合MBSs之后,又可以使反共振消失转而出现新的共振峰.     

氮分子B3Πg激发态的光谱研究

在较低气压(4Torr)条件下采用直流辉光放电激发氮分子气体,得到了氮分子放电等离子体在320～470nm范围内的发射谱,其形状为一等间隔的谱线序列,并沿长波方向谱线强度逐渐变小。通过计算分析对谱线进行了标定,确定该组谱线是由处于C^3Πg激发态低振动能级的氮分子向B^3Πg态不同振动能级的辐射跃迁所产生;在此基础上计算出氮分子B^3Πg态的振动频率为1738．50cm^-1。结合相关的能级参数计算了C^3Πg(v=0)→B^3Πg(v″=0～5)之间的Frank-Condon跃迁因子,实验所得的谱线强度与之符合得很好。     

四氯化碳ν_1振动在费米共振光谱特性参数中的作用

研究了CCl4的ν1+ν4与ν3的费米共振现象。结果表明ν1振动频率是影响费米共振红外和拉曼光谱特性参数(峰位差Δ,耦合系数W,光谱强度比R,非谐力常数K等)的主要因素,而其光谱强度大小却与这些参数无直接关系。本文用Berttran理论和群论对这一结果给以解释。该研究对理解费米共振现象和分子结构研究中的谱线归属等有参考价值。     

对苯醌络合物对费米共振的影响

费米共振现象不仅存在于简单化合物中,复杂的络合物振动光谱中同样存在。简单化合物“加和”形成络合物,分子间某些基团的特性也随之改变,分子光谱就会产生明显的变化。在一定条件下,对苯醌与脯氨酸能够形成电子转移络合物,但其拉曼光谱强度比较小,采用Teflon液芯光纤可以获得高质量的共振拉曼光谱。实验分别获得了对苯醌和其络合物的拉曼光谱图,利用J.F.Bertran量子力学微扰理论,对分子的费米共振特性进行分析。结果表明,络合物的形成使得CO键的费米共振峰向高波数方向移动,拉曼光谱强度比减小,频率间隔增大,耦合系数增大。这种变化的原因解释为,混合溶液中,脯氨酸作为给体,苯醌作为受体,脯氨酸中的N原子上的非成键电子转移到对苯醌的π反键轨道上形成了n—π*电子转移络合物,使分子的振动能级发生了变化。这些分析为研究大分子、络合物以及聚合物的谱线认证、归属提供了新的思路和线索。     

四氯化碳v1振动在费米共振光谱特性参数中的作用

研究了CCl4的v1＋v4与v3的费米共振现象。结果表明v1振动频率是影响费米共振红外和拉曼光谱特性参数（峰位差△，耦合系数W，光谱强度比R，非谐力常数K等）的主要因素，而其光谱强度大小却与这些参数无直接关系。本文用Berttran理论和群论对这一结果给以解释。该研究对理解费米共振现象和分子结构研究中的谱线归属等有参考价值。     

Influence of pressure effect on Fermi resonance in binary solution

The Fermi resonance behaviours of the two groups of binary solutions --- pyridine and methanol, benzene and carbon tetrachloride, under different pressures are investigated according to their Raman spectra. The effect of pressure on Fermi resonance in binary solution differs significantly from that in pure liquid. In a binary solution, with the intermolecular distance shortening, the intermolecular interaction potential increases, the shift rates of the Raman spectral lines increase, the spectral line splitting occurs ahead of that in pure liquid, and the wavenumber separation Δ₀ between the unperturbed harmonic levels shifts more quickly, too. The Fermi resonance parameters, the coupling coefficient W and the intensity ratio R of the two Raman bands, decrease rapidly with pressure increasing, and the pressure at which Fermi resonance phenomenon disappears is much lower than that in pure liquid, especially in the solution whose molecules are of the same polarity. This article is valuable in the identification and the assignment of spectral lines under high pressure, as well as the study of high pressure effect, intermolecular interaction, and solvent effects in different cases, etc.     

分子费米共振拉曼光谱强度分析

测量了CCl₄和CS₂分子的Raman光谱。用Bertran理论和群论等相关理论对其光谱强度进行了分析,获得了发生费米共振分子的拉曼光谱强度的特殊规律： (1)发生费米共振的基频和倍频(和频)间发生能量转移,两光谱强度大小相互接近,当发生费米共振的基频和倍频(和频)间距离很小时,两发生费米共振的光谱强度相等(R=1);(2)能出现倍频光谱强度高于其基频光谱强度;(3)也会观测到费米共振光谱,而观测不到参与费米共振的和频中的基频光谱。此研究对化学、材料科学中的分子结构、材料成分等研究中的谱线认证、归属有很好的参考价值。     

Perceptual interaction of the harmonic source and noise in voice

Although the amount of inharmonic energy (noise) present in a human voice is an important determinant of vocal quality, little is known about the perceptual interaction between harmonic and inharmonic aspects of the voice source. This paper reports three experiments investigating this issue. Results indicate that perception of the harmonic slope and of noise levels are both influenced by complex interactions between the spectral shape and relative levels of harmonic and noise energy in the voice source. Just-noticeable differences (JNDs) for the noise-to-harmonics ratio (NHR) varied significantly with the NHR and harmonic spectral slope, but NHR had no effect on JNDs for NHR when harmonic slopes were steepest, and harmonic slope had no effect when NHRs were highest. Perception of changes in the harmonic source slope depended on NHR and on the harmonic source slope: JNDs increased when spectra rolled off steeply, with this effect in turn depending on NHR. Finally, all effects were modulated by the shape of the noise spectrum. It thus appears that, beyond masking, understanding perception of individual parameters requires knowledge of the acoustic context in which they function, consistent with the view that voices are integral patterns that resist decomposition.     

Luminescence and Energy Transfer in Frozen Solutions of Uranyl Sulfate in Selective Excitation

Luminescence spectra of vitrified solutions of uranyl sulfate in a concentrated sulfuric acid are investigated in the range 4.2–80 K in selective laser excitation. It is shown that the luminescence spectra are a superposition of two components — the component that is related to the resonance excitation of uranyl complexes and the component that is caused by the luminescence of uranyl complexes sensitized by the transfer of electron-excitation energy from the resonance-excited centers. The nonselective character is established for the spectral migration of electron-excitation energy with participation of the bending vibrations of the uranyl complex that ensure direct vibrational transitions between neighboring electronic energy levels. The temperature evolution of the luminescence spectra can be described within the framework of the model of configuration coordinates with allowance for only the linear terms of vibronic interaction.     

激光诱导击穿光谱法铁基合金谱线选择研究

内标法是激光诱导击穿光谱(LIBS)最常用的定量分析方法之一。为了提高定量分析精度，研究了谱线强度比的相对波动特性随分析线和内标线之间激发能级差(ΔE)和波长差(Δλ)变化的规律。在局部热力学平衡条件下，建立了考虑等离子体中某元素电子上能级跃迁到下能级产生原子发射谱线的激发能级差、等离子体温度、配分函数和离子密度等强度影响因素的数学模型，对模型中激发能级差对谱线强度相对波动的影响进行了研究。得到在-2 eV<ΔE<2 eV和等离子体温度范围在3 000～15 000 K条件下，谱线强度随着ΔE和T变化的趋势：随着ΔE变大，谱线强度比呈上升，在ΔE=2 eV，T=3 000 K时谱线强度比最大；并且谱线强度比相对波动对ΔE和T敏感，ΔE趋近于零时相对波动变小，T对谱线强度比相对波动影响变化不大，整体趋势平稳。在T=10 000 K时，ΔE<0相对波动比ΔE>0时小，因此理论上优先选择ΔE<0的谱线对。通过理论分析得出|ΔE|越接近于零，谱线强度比相对波动越小。实验装置中采用工作波长1 064 nm，脉冲能量85 mJ，重复频率1 Hz，脉冲宽度13 ns的Nd∶YAG脉冲激光诱导击穿样品；采用工作波长200～975 nm，光学分辨率优于0.05 nm的Andor公司Mechelle 5000光谱仪，配合Andor New iStar型号ICCD采集光谱；利用激光诱导铁基合金等离子体光谱进行验证。实验中，以Fe为内标元素，Cr和Mn为分析元素。筛选NIST谱线库中跃迁概率在106以上的谱线，并优先选择共振线能级差相近的非共振线进行对比分析。结果表明，选择激发能级相近或波长相近的谱线作为分析谱线的原则有一定的局限性。对于Cr和Fe，|ΔE|在0.14和1.51 eV时得到的谱线强度相对标准偏差(RSD)分别为6.7%和4.6%，其谱线强度比理论值和实际值之差分别为1.14和0.59；|Δλ|在11.7和50.8 nm时得到的RSD分别为6.3%和4.4%，其谱线强度比理论值和实际值之差分别为1.69和0.62。分析表明，相比于波长差，激发能级差对Cr/Mn相对波动影响较大。分析元素Cr/Mn与内标元素Fe波长差绝对值不断增大，RSD反而不断减小；在1.50 eV和90 nm较大约束范围内，|ΔE|大的谱线得到的谱线强度比相对波动相对较小，Cr和Fe的RSD最大相差为2.06%；|Δλ|大的谱线得到的谱线强度比相对波动相对较小，Cr和Fe的RSD最大相差为1.35%。由以上实验结果得出，在实际选择分析谱线时，尽量选择激发能级和波长相近的谱线原则有一定的局限性。|ΔE|或|Δλ|大的谱线得到的RSD较小，选择谱线强度比理论值和实际值最接近的谱线可以作为谱线选择依据。另外，选择谱线强度比理论值和实际值最接近的谱线，可以降低谱线强度比相对波动。     

Photoemission and the electronic structure of PuCoGa5

The electronic structure of the first Pu-based superconductor PuCoGa5 is explored using photoelectron spectroscopy and a novel theoretical scheme. Exceptional agreement between calculation and experiment defines a path forward for understanding the electronic structure aspects of Pu-based materials. The photoemission results show two separate regions of 5f electron spectral intensity, one at the Fermi energy and another centered 1.2 eV below the Fermi level. The results for PuCoGa5 clearly indicate 5f electron behavior on the threshold between localized and itinerant. Comparisons to delta phase Pu metal show a broader framework for understanding the fundamental electronic properties of the Pu 5f levels in general within two configurations, one localized and one itinerant.     

改变溶液折射率方法研究Fermi共振

Fermi共振现象在光谱分析中的谱线认证、归属有重要应用,然而,它蕴含的丰富物理规律、内容及研究方法亟待开发和研究.本文提出了一种改变溶液折射率研究Fermi共振的方法,该方法以Onsager电介质极化理论为依据,利用分子在溶液中的Raman散射强度(散射系数)随溶液折射率的变化来研究Fermi共振规律.该方法不仅能给出Fermi共振各参数间及与溶液折射率之间的关系,而且发现了Fermi共振双峰的非对称移动、倍频的基频也受Fermi共振调谐等现象.为全面认识Fermi共振规律提供了一种研究方法.     

Electronic structure of 1 ML NTCDA/Ag(1 1 1) studied by photoemission spectroscopy

We performed high-resolution photoemission experiments at different photon energies to investigate the valence band structure of 1 ML of 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTCDA) on Ag(1 1 1). Besides the known occupied molecular orbitals HOMO and HOMO − 1 we observe a new state close to the Fermi level, which results from the interaction between NTCDA and the substrate, partially filling the lowest unoccupied orbital of the free molecule (LUMO) in the monolayer system. By tuning the photon energy through the carbon K-edge, a resonance like change of the spectral intensity at the HOMO and HOMO − 1 energies is clearly revealed, which we use for an assignment of the individual spectral features to a predominant localization either at the naphthalene core or the anhydride group.