基于极紫外自由电子激光的中性团簇红外光谱（英文）

团簇在能源催化和大气雾霾等诸多化学过程中广泛存在,团簇表征与性能研究对诠释化学反应机理至关重要.然而,中性团簇由于缺乏电荷、难于探测,实验研究非常困难.鉴于上述情况,发展了基于极紫外自由电子激光的中性团簇红外光谱实验方法,用于质量选择中性团簇的高灵敏探测、结构表征和性能研究.红外-极紫外衰减和红外+极紫外增强光谱实验方法已被应用于一些中性水团簇和一些中性金属羰基化合物的研究.由于极紫外自由电子激光的波长范围涵盖了绝大多数中性团簇的第一电离势,这一独特的实验方法为开展各类中性团簇红外谱学和结构的研究打开了大门.本文综述了这些红外光谱实验方法及其在中性团簇研究中的应用.     

阿尔法蒎烯臭氧分解反应的极紫外自由电子激光光电离质谱研究

阿尔法蒎烯是大气中含量最高的自然源萜类挥发性有机物,其臭氧化分解反应会产生大量的反应中间体和产物,精确表征这些物种被认为是大气化学最前沿、最具挑战性的课题之一. 本文利用极紫外自由电子激光光电离质谱方法,研究了阿尔法蒎烯的臭氧分解反应机理. 该反应是在2立方米的烟雾箱中进行,利用气动透镜把产生的气溶胶传输到质谱探测腔室,利用极紫外自由电子激光对气溶胶进行单光子软电离,测得了常规实验方法难以得到的飞行时间质谱,发现了一系列新物种. 与量子化学理论计算相结合,揭示了这些新物种的反应机理. 这些研究结果从分子水平上揭示了蒎烯的臭氧分解反应机制,有助于理解大气雾霾微观机理.     

基于旋转相干光谱的整形飞秒激光转动动力学调控

我们实验上发展了基于飞秒激光旋转相干光谱的整形飞秒激光转动动力学调控方法，通过脉冲整形技术调控激发脉冲的光谱相位，从而实现对飞秒激光作用下转动态相干激发过程中复原信号及转动布居数的调控. 研究了飞秒激光旋转相干光谱对激光频谱相位的响应机制，突出了飞秒激光频谱相位在气相分子转动态相干激发中的重要作用. 为飞秒激光作用下生物大分子和团簇鉴别及结构探测研究提供了新的参考.     

硼化铝团簇Al-B_n(n=2～9)的密度泛函理论研究

基于密度泛函理论(Density Functional Theory,DFT),对中性硼化铝团簇AlBn(n=2～9)的几何结构、稳定性以及红外振动光谱进行了理论研究,讨论了他们的不同点及AlB4、AlB5、AlB6和AlB7的基态构型和相对稳定性.对于中性AlBn(n=2～9)基态构型,对比讨论了其失去[AlBn+(n=2～9)]和得到[AlBn-(n=2～9)]一个电子后化学键强度的变化、掺入铝原子的影响以及团簇几何结构的演化.计算结果表明:虽然掺入Al之后,团簇的稳定性差异变小,但是硼团簇和硼化铝团簇都趋向于形成平面、准平面结构以获得更大的稳定性;硼团簇的构型对硼化铝团簇的结构和稳定性起着决定性的作用;AlB3、AlB5和AlB8更稳定;红外光谱的振动模式倾向于B原子和对称性优先的趋势.     

AlB+n(n=2~10) 团簇结构和红外振动光谱研究

用密度泛函理论的B3LYP方法在6-311G(d)水平上对AlB+n（n=2~10）团簇几何结构、稳定性、电子结构和成键特性进行了系统理论研究,得到了AlB+n（n=2~10）团簇的最稳定结构.结果表明,硼原子间容易聚集,铝原子处于整个硼原子集团的外围.与相应中性AlBn团簇相比,Al-B键作用变弱,使正价团簇（n=6和10除外）结构变化较大|对AlB+n（n=2~10）和相应中性团簇能隙的计算分析表明,AlB+n 团簇的稳定性有所增强,其中AlB+3、AlB+5和AlB+8团簇尤为显著|通过对最稳定构型红外振动光谱的研究分析表明,硼原子间对称或非对称振动、铝原子不动的振动模式更容易出现较强谱峰,即硼原子间更容易成键.     

Bi靶激光等离子体极紫外光源以及碎屑辐射特性研究

激光等离子体极紫外光源具有体积小、稳定性高和输出波长可调节等优势,在极紫外光刻领域发挥着重要的作用。Bi靶激光等离子体极紫外光源在波长9～17 nm范围内具有较宽的光谱,可应用于制造极紫外光刻机过程中所需的极紫外计量学领域。利用平像场光谱仪和法拉第杯对Bi靶激光等离子体极紫外光源以及离子碎屑辐射特性进行了实验研究。在单脉冲激光打靶条件下,实验中观察到Bi靶激光等离子极紫外光谱在波长12.3 nm处出现了一个明显的凹陷,其对应着Si L-edge的吸收,是Bi元素光谱的固有属性。相应地在波长为11.8和12.5 nm位置处产生了两个宽带的辐射峰。研究了两波长光谱特性以及辐射强度随激光功率密度的变化。结果表明,在改变聚焦光斑大小实现不同激光功率密度（0.7×1010～3.1×1010 W·cm-2）过程中,当功率密度为2.0×1010 W·cm-2时两波长处的光辐射最强,其原因归结为Bi靶极紫外光辐射强度受激光能量用于支撑等离子膨胀的损失和极紫外光被等离子体再吸收之间的平衡制约所致。在改变激光能量实现不同激光功率密度过程中,由于烧蚀材料和产生两波长所需高阶离子随着功率密度的增加而增加,增强了两波长处的光辐射。进一步,研究了双脉冲激光对Bi靶极紫外光谱辐射特性影响,实验发现双脉冲打靶下原来在单脉冲打靶时出现在波长13～14 nm范围内的凹陷消失。最后,对单脉冲激光作用Bi靶产生极紫外光源碎屑角分布进行了测量。结果表明,当探测方向从靶面法线方向移动到沿着靶面方向上的过程中,探测到Bi离子动能依次减小,并且离子动能随激光脉冲能量降低而呈线性减小。此项研究有望为我国在研制极紫外光刻机过程所需的计量学领域提供技术支持和打下夯实的基础。     

温度对LiCl/(DMSO-H_2O)溶液影响的2D-IR研究

对溶液的研究,尤其是金属离子在双溶剂溶液中的研究是化学化工和环境科学等领域的重要环节。传统的溶液分析方法主要是利用一维红外光谱或拉曼光谱等进行分析,但其分辨率低,误差较大,谱峰重叠严重,难以对复杂的体系进行研究。采用二维红外光谱和密度泛函理论相结合的方法,以实现对溶液内团簇的准确分析。利用傅里叶变换红外光谱仪,温度为外扰条件,在4 000～400 cm~(-1)范围内分别对双溶剂DMSO-H_2O和Li~+/(DMSO-H_2O)溶液体系进行红外光谱实验。对所得数据进行归一化等处理,获得SO双键的一维红外光谱图,发现水的加入使DMSO的SO红外光谱发生了红移,且随着温度的升高SO红外振动强度逐渐增加, Li~+加入使得SO双键强度整体下降,其谱峰重叠严重,难以分析。利用二维红外光谱对溶液中团簇内分子SO双键的类型、动态变化、变化顺序以及锂离子对其的影响进行分析,获得其变化规律,解决了一维红外光谱存在的问题。结合密度泛函理论计算对团簇结构进行优化和分析,证明二维红外光谱分析结果的正确性和可行性,实现理论计算与实验的相互印证,拓宽二维红外光谱与密度泛函理论的研究领域。实验以温度为扰动,针对DMSO-H_2O和Li~+/(DMSO-H_2O)溶液中团簇内分子SO双键的变化,运用二维红外光谱探讨溶液中微团簇变化规律。研究发现,温度扰动时,溶液的二维同步红外光谱中,在1 010, 1 045, 990和1 020 cm~(-1)附近有四个自动峰,说明溶液中团簇内存在甲基的振动, DMSO·H_2O、单体以及二聚体DMSO分子团簇的振动;二维异步红外光谱中,发现1 010 cm~(-1)的DMSO·H_2O较先变化,说明该团簇对温度扰动更加敏锐。结果表明,结合密度泛函理论计算和二维红外光谱分析能较好地了解溶液中团簇的存在形式及温度扰动对它们的影响与变化规律,实现了一维光谱中由于峰的重叠或变化不明显等对化学信号的提取。     

Mg_2Si_n(n=1～9)团簇结构、稳定性与光谱性质的密度泛函理论研究

运用密度泛函理论(DFT)中的B3LYP方法,在6-311G(d)基组的水平上对Mg2Sin(n=1~9)团簇的多种可能几何构型进行了结构优化,获得了各个尺寸下团簇的最低能量结构,随后对最低能量构型的稳定性、红外光谱与拉曼光谱性质进行了理论研究。结果发现:当n≥3时,Mg2Sin团簇的基态构型均为立体结构;Mg原子的掺入提高了体系的化学活性;Mg2Si4与Mg2Si6是幻数结构;在相同的观察频段内,Mg2Si4团簇的红外光谱只有一个强振动峰,拉曼光谱强振动峰的个数较多且位于高频段内,其拉曼活性较强,与之相反,Mg2Si6团簇的红外光谱强振动峰个数较多,而拉曼光谱强振动峰则只有一个,表明其红外活性较强。     

质子化丙酮分子团簇的结构和振动光谱

用密度泛函B3LYP/ 6 3 1G(d)方法 ,对质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)弱相互作用体系进行了全自由度能量梯度优化 ,得到了该系列团簇的稳定结构及其对应的体系能量 .通过对构型的分析得出了质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)的生长规律 .计算了中性丙酮分子团簇体系的质子亲合能并总结出其变化趋势 .分析讨论了质子化团簇的红外振动光谱 ,发现质子化团簇的振动光谱普遍较中性环型团簇的振动光谱复杂 ,最强的振动峰来源于质子在溶剂壳中两个氧原子之间的振动 ,而且随着团簇尺寸的增加羰基的伸缩振动峰的数目也随之增多     

超短强激光脉冲激励甲烷团簇的内电离机理

采用三维粒子动力学模拟方法研究了甲烷团簇在超短强激光脉冲激励下的爆炸动力学行为,重点讨论了几种典型的内电离机理对团簇爆炸过程中离子的价态和动能的影响.研究表明,在激光脉冲强度比较小的情况下,团簇中的原子主要是在光场作用下通过隧道电离的方式发生电离.当激光场进一步增强时,势垒压低电离是电离的主要方式.在相同的较高激光强度下,团簇更容易通过势垒压低电离达到高的电离价态.团簇发生电离后,其内部库仑电场的点火电离效应和内部滞留自由电子的碰撞电离效应也将增强团簇的再次电离过程. 关键词： 超短强激光脉冲 甲烷团簇 内电离     

Luminescence properties of silver zinc phosphate glasses following different irradiations

We report on exposing a photosensitive zinc phosphate glass containing silver to different radiation (electron, gamma, optical). Laser irradiations using nanosecond ultraviolet (UV) and femtosecond infrared (IR) laser are compared with gamma and electron exposure. All irradiated glasses exhibit absorption maxima around 320 nm and 380 nm and emission in the visible spectral range. Following exposure, silver clusters are formed. The optical response of such species is investigated using absorption and fluorescence spectroscopic techniques. The mechanism of formation of these clusters is discussed.     

Two-color photoionization and photoelectron studies by combining infrared and vacuum ultraviolet

Recent developments of two-color infrared (IR)-vacuum ultraviolet (VUV) and VUV-IR photoionization and photoelectron detection schemes for spectroscopic studies are described. By preparing molecules in selected rovibrational states by IR excitation prior to VUV-photoionization, state-selected and state-to-state photoionization cross sections can be obtained by IR-VUV-photoionization efficiency (IR-VUV-PIE) and IR-VUV-pulsed field ionization-photoelectron (IR-VUV-PFI-PE) measurements, respectively. Rotationally resolved autoionizing Rydberg states converging to excited ionic states, which cannot be observed by single-photon VUV-PIE measurements, can be examined by the IR-VUV-PIE scheme. By monitoring the photoion and the PFI-PE intensities at a fixed VUV energy as a function of IR frequency, the respective IR photoion and IR absorption spectra of the corresponding neutral molecule can be measured. Two-color VUV-IR photo-induced Rydberg ionization (PIRI) experiment, in which high-n Rydberg states are prepared by VUV-photoexcitation followed by IR-induced autoionization, has also been demonstrated. Since the IR-VUV-PIE, IR-VUV-PFI-PE, and VUV-IR-PIRI methods do not require the existence of a bound intermediate electronic state in the UV and are generally applicable to all molecules, the development of these two-color photoionization and photoelectron schemes is expected to significantly enhance the scope of VUV spectroscopy and chemistry.     

Structure determination of gas-phase niobium and tantalum carbide nanocrystals via infrared spectroscopy

Niobium and tantalum carbide clusters have been isolated in the gas phase and irradiated with intense tunable infrared (IR) light. Stable neutral clusters are selectively ionized and subsequently detected in a mass spectrometer. By tuning the IR frequency, infrared multiphoton absorption spectra are obtained for a whole range of clusters. These mass-selective IR spectra lead to insights into the structures of small niobium and tantalum carbide clusters and nanocrystals.     

Experimental intercomparison of the absorption cross-sections of nitrous acid (HONO) in the ultraviolet and mid-infrared spectral regions

Nitrous acid, HONO, is an important trace gas in tropospheric photochemistry, because it is a source of OH radicals. In order to obtain HONO concentrations from spectroscopic measurements, the knowledge of accurate absorption cross-sections is essential. Furthermore, the ultraviolet absorption cross-sections of HONO determine its atmospheric photolysis rates, which are still being debated. In particular, in a recent field study focusing on the photolysis frequency of HONO, the absolute values of the ultraviolet absorption cross-sections have been proposed as a potential source for systematic errors. For these reasons, we have compared the absorption cross-sections for HONO in the infrared (IR) and ultraviolet (UV) by performing simultaneous measurements in both spectral regions. Assuming that the IR cross-sections (that show good agreement between different studies) are correct, our study shows a good agreement between the consistent infrared studies and some selected accurate UV spectra published previously (about 6%) while a rather large disagreement (about 22%) is observed when using other UV data sets.     

Vibrational predissociation of SF6 dimers and trimers

IR photo-dissociation spectra of SF₆ clusters have been studied. A He-seeded molecular beam has been attenuated by crossing it with a line tunable cw CO₂ laser of moderate power. — In the electron bombardment beam ionizer (E _el=100eV) small neutral clusters are found to fragment predominantly to the main monomer mass (SF ₅ ⁺ ). — Predissociation spectra have been calculated for clusters containing up to six SF₆-molecules invoking the dipole-dipole resonance force to lift the degeneracy of the molecule — excited molecule interaction. On the basis of these spectra, dimer and trimer concentrations have been determined quantitatively, for different molecular beam conditions.     

Multistep ionization of argon clusters in intense femtosecond extreme ultraviolet pulses

The interaction of intense extreme ultraviolet femtosecond laser pulses (lambda = 32.8 nm) from the FLASH free electron laser (FEL) with clusters has been investigated by means of photoelectron spectroscopy and modeled by Monte Carlo simulations. For laser intensities up to 5x10(13) W/cm(2), we find that the cluster ionization process is a sequence of direct electron emission events in a developing Coulomb field. A nanoplasma is formed only at the highest investigated power densities where ionization is frustrated due to the deep cluster potential. In contrast with earlier studies in the IR and vacuum ultraviolet spectral regime, we find no evidence for electron emission from plasma heating processes.     

Metal-based transparent heat mirror for ultraviolet curing applications

Metal-based transparent heat mirror for ultraviolet curing applications was designed in terms of induced transmission principle, good ultraviolet transparency and high infrared ray (IR) reflection properties can be obtained by the means of optimal layers design. After a comprehensive analysis to materials properties, TiO₂/Ag/TiO₂ nano-multilayers with a Ultraviolet (UV) transmission of 81% (at 365 nm) and an IR reflectivity of 90% (at 1600 nm) were designed and prepared by conventional evaporation. The multilayers exhibit a sharp interface between dielectric and metal layers by spectroscopic ellipsometry analysis. The experiment results prove that critical thickness of metal layer determined in light of admittance match and skin effect has no applicable meaning in long-wavelength UV region. Dependence of transmittance in near UV spectra on the thickness of metal layer is less sensitive than that in near IR. This transparent heat mirror can be applied in the “windows” of ultraviolet curing system for heat insulation.     

High-Resolution Infrared-Vacuum Ultraviolet Photoion and Pulsed Field Ionization-Photoelectron Methods for Spectroscopic Studies of Neutrals and Cations

扫描单模红外光参量振荡(IR-OPO)激光器的波长激发待测分子,并用固定波长的真空紫外(VUV)激光器光电离(PI)探测被红外激发的分子,可获得高灵敏度的中性多原子分子的高分辨红外光谱. 这种方法(IR-VUV-PI)基于真空紫外光电离作为探测,可分辨样品中的不同成分,因此适用于对含同位素,自由基,络合物等通常为非纯的样品进行红外光谱研究. 高分辨的IR-VUV-PI谱可实现对分子单一振转态的选择,在选态的基础上进行真空紫外脉冲场电离零动能光电子谱(VUV-PFI-PE)的研究,可得到高分辨振转解析的光电子谱.被研究的分子包括一卤代甲烷(CH3X(X=Br,I)),乙烯(C2H4),丙炔(C3H4)等. 实验表明,采用高分辨的单模红外光参量振荡器代替先前使用的低分辨红外光参量振荡器可显著的提高IR-VUV-PI和IR-VUV-PFI-PE谱的信噪比. 并进一步讨论了采用IR,VUV,分子束三束同轴以提高IR-VUV-PI和IR-VUV-PFI-PE谱灵敏度的方案.     

L—fucose的光谱研究

探测了低２下的Ｌ－ｆｕｃｏｓｅ的红外光谱、Ｒａｍａｎ光谱、紫外吸收光谱和紫外荧光光谱。证实紫外荧光光谱较为灵敏，探讨了其作为癌症早期诊断的简便、迅速、廉价、无痛苦方法的可能性。     

第一性原理研究荷电状态对Pd_(13)团簇催化分解NO性能的影响

文章运用了第一性原理计算方法研究一氧化氮在中性和带电荷背景的Pd_(13)团簇上的吸附和分解.研究结果表明:NO在中性和带电荷的Pd_(13)团簇上均倾向于吸附在Pd_(13)团簇的空位.带负电的Pd_(13)团簇比中性、带正电的Pd_(13)团簇对于NO的催化分解更有利,体现在带负电的Pd_(13)团簇上有更强的吸附能和更低的反应能垒.