金团簇结构和电子性质的密度泛函研究

采用密度泛函理论,研究了Aun(2≤n≤10)团簇的最优结构和电子性质.采用各种不同的拓扑结构进行优化,计算结果显示最优结构都是二维的;在得到的最优结构基础上,进一步研究了其电子性质.结合能的二阶差分,费米能和能隙都显示了奇偶谐振效应.具有偶数个原子的金团簇要比奇数个原子的金团簇稳定,这与金团簇中的电子配对紧密相关.     

磁控溅射法制备金团簇纳米颗粒及性能表征

 采用磁控溅射法制备金团簇纳米颗粒,用透射电镜(TEM)、X射线衍射(XRD)、紫外可见光分光光度计(UV-Vis)和X射线光电子能谱(XPS)等分析手段对其表征,研究了金团簇纳米颗粒的形貌、颗粒度、结构、光吸收性质及物质成份。研究结果表明：制备的金团簇纳米颗粒呈球形,平均粒径在10 nm左右,粒径分布均匀,无团聚、氧化现象,颗粒的结构为面心立方。在519 nm处出现团簇颗粒的表面等离子共振吸收峰,测试得到Au(4f_7/2)和Au(4f_5/2)电子的结合能分别为83.3 eV和86.9 eV,并且没有出现金的氧化产物。     

电场辅助溶解法实现玻璃表面金纳米粒子的形貌控制

贵金属纳米粒子由于其非常独特的光学特性和表面活性, 在光子学、 催化和生物标识等方面都有非常重要的应用. 采用离子溅射和后续热处理相结合的方法在玻璃表面形成了尺寸大约为60-80 nm的单分散的球形金纳米粒子. 在适当的温度条件下, 采用步进式增加的强直流电场, 实现了金纳米粒子的电场辅助溶解过程. 在玻璃表面的不同颜色区域, 初始球形的金纳米粒子溶解成月蚀状形貌. 结合不同颜色区域内金纳米粒子的表面等离子体共振吸收性质和扫描电镜照片, 研究了实验条件对金纳米粒子性质的影响. 结合电场辅助溶解实验过程中的电流-电压特性, 分析了金纳米粒子在强直流电场辅助下溶解的物理过程: 金粒子中动出的电子向阳极的隧穿过程作为开始, 随后是金阳离子向玻璃基体中的传输过程和阴极提供的电子与带有正电荷的金粒子相结合的过程. 详细讨论了电场辅助溶解法实现金纳米粒子形貌控制的物理机制.     

Fe基体中包含Cu团簇的Fe-Cu二元体系在升温过程中结构变化的原子尺度计算

采用基于嵌入原子方法的分子动力学方法模拟了具有体心立方晶格结构的Fe基体中包含小尺寸Cu纳米粒子的Fe-Cu二元体系在升温过程中的原子堆积结构变化.进行了Cu原子均方位移、Cu原子对分布函数和原子的径向密度分布函数的计算,并对纯Cu原子区、Fe-Cu界面区和纯Fe基体区的分区域原子堆积结构进行了分析.结果表明,Fe基体内Cu团簇的尺寸及其在Fe基体内所能占据区域的大小,对不同温度下的Cu团簇内原子堆积结构及Fe基体的原子堆积结构具有影响.升温过程中不同尺寸受基体约束Cu团簇对Fe基体结构改变的影响表现出很大差异.对于Fe_(bulk)-Cu_(135)体系,基体的应变临近Fe-Cu界面区,同时在团簇中间的基体区域出现大量空位缺陷和应变集中区;对于Fe_(bulk)-Cu_(141)体系,随温度升高,基体中出现的应变区域表现为小尺寸、数量多向大尺寸、小数量的变化.     

组氨酸、谷胱甘肽混合修饰金纳米团簇的光稳定性研究

金纳米团簇(简称金簇)由几到几百个金原子及修饰试剂组成,由于其尺寸接近于电子费米波长,表现出良好的发光特性及生物相容性,是一类新型纳米标记探针。目前,金纳米团簇在生物检测、细胞成像、癌症诊断及治疗等领域受到研究者的广泛关注。然而,对于光照条件下金簇的稳定性还不清楚。在合成组氨酸、谷胱甘肽混合修饰金簇的基础上,系统研究了光照条件下金簇在不同pH(5.0,7.4和9.0)的荧光变化规律,结果表明,在氙灯强光照射下,金纳米团簇的荧光会随着照射时间的增加逐渐降低,在pH 9.0条件下比pH 5.0及7.4时降低更快,说明金簇在pH 5.0及7.4时光稳定性更好。在此基础上,采用紫外-可见吸收光谱、红外光谱等手段研究了光照前后金簇表面基团的变化规律,发现光照后金簇的紫外可见吸收光谱及红外光谱均发生了明显的变化,说明光照导致金簇表面修饰基团发生了变化。当向体系中通入氮气后,金簇最大发射波长处荧光强度随照射时间的变化明显变慢,说明金簇表面基团与溶液中溶解氧发生了反应,导致金簇表面电荷及修饰试剂状态发生变化,从而导致金簇荧光产生猝灭。相关研究结果对于金纳米团簇在生命科学及分析化学等领域的进一步应用具有一定的参考价值。     

PSP—SA模拟金团簇的几何结构与基态能量

采用基于模拟退火的粒子群智能算法(PSO-SA)和紧束缚二阶动量矩势函数(TB-SMA)对金团簇Aun(n≤10)的基态能量、结构及其随团簇尺寸变化的规律进行了研究.结果表明n为偶数的金团簇的结构比邻近为奇数的金团簇稳定,具有"奇-偶"振荡效应;由金团簇基态能量的二阶差分可以看出Au4、Au6、Au8结构比较稳定,具有"幻数"效应.     

光解水的原子尺度机理和量子动力学

利用阳光直接将水分解为不含碳的氢气燃料和氧气是面向全球能源危机环保且低成本的解决方案.得益于电子结构理论和量子模拟方法的进步,人们已经能够直接研究在纳米颗粒上等离激元诱导光解水过程在原子尺度上的反应机理和超快动力学.本文简述近年来的相关工作进展.吸附在氧化物薄膜上的金纳米颗粒很有希望成为水分解的高效新型光催化剂.在光激发条件下,水分解反应速率和光强、热电子转移之间有强相关性.水分解速率不仅取决于光吸收强度,还受到等离激元量子振动模式的调控.这对于太阳能光解水器件中纳米颗粒的设计有借鉴意义.我们发现液态水在金团簇等离激元催化下100 fs内就能产生氢气.超快量子动力学模拟表明,该过程中场增强起主导作用,从金属到水反键态的超快电荷转移也扮演着重要角色.综合这些原子尺度上的量子动力学研究,我们提出受激水分子中氢原子高速碰撞(速度远远超出其热速度)合成氢分子的"链式反应"机理.     

金纳米粒子光学性质中的尺寸和形状效应

纳米尺度的金属及半导体呈现出特殊的光学、电学及磁学性质,采用近年发展起来的离散偶极近似(DDA)的方法,我们分析了金纳米粒子的尺寸及形状对其光学性质的影响。粒子周围介质的影响在文中亦作了分析。计算结果显示,金纳米粒子的等离子体吸收带同时受到粒子尺寸和形状的影响,但来自形状的影响更为明显。与米氏理论及扩展的甘氏理论相比较,DDA方法在粒子尺寸不再远小于入射光波长的时候更准确,并能应用于任何形状的纳米粒子。理论计算与实验结果能较好的吻合。     

基于金属-配体共轭界面键的纳米粒子内电荷离域:金属d电子的影响（英文）

过去研究表明,当金属纳米粒子被有机配体修饰形成界面共轭的"金属-配体"共价键时,会出现特殊的粒子内电子离域现象,然而对于不同金属对此现象的影响却缺少系统研究.本文介绍了合成了乙基苯乙炔修饰的d区元素(包括4d的钌、铑和钯,5d的铱、铂和金)纳米粒子的方法,并通过对比研究其光电性质,阐明了金属元素d电子对其粒子内电子离域现象的影响.傅里叶转换红外光谱和光致发光光谱测量结果均表明,在同一周期的金属元素中,随着d电子数的增加,粒子内电子离域现象逐渐增强.然而钯却表现异常,这可能与其异常低的电子亲和能相关.     

基于金纳米粒子增强有机-无机杂化钙钛矿放大自发辐射

有机-无机杂化钙钛矿作为激光的增益介质时,存在室温时纳秒脉冲或连续激光作用下的光泵浦器件不稳定、难以实现电泵浦激光等问题.通过将金纳米粒子水溶液和PEDOT∶PSS溶液共混的方法,将20nm尺寸的金纳米粒子掺杂至光泵浦平面波导器件的界面层PEDOT∶PSS中,掺杂了金纳米粒子的平面波导器件(以CH_3NH_3PbBr_3为增益介质)的放大自发辐射绝对强度相对于没掺杂金纳米粒子的器件提升了5.5倍.实验结果表明,金纳米粒子的引入,一方面提升了CH3NH3PbBr3薄膜的吸收,增加了粒子反转数目,另一方面加快了激发态激子的辐射跃迁速率.仿真分析表明,金纳米粒子的近场和远场复合表面等离激元可有效耦合增益介质光吸收/发射主区域,从而提高了平面波导器件的放大自发辐射性能.研究结果可为高效泵浦激光的实现提供参考.     

Structural transitions in small nickel clusters

The processes of a thermal impact on Ni nanoclusters with a radius of up to 0.8 nm have been studied by means of molecular dynamics with the use of a tight-binding potential. The simulation indicates that the structural transition from the initial fcc phase to the icosahedral modification occurs under the influence of temperature. The transition temperature is shifted towards the cluster melting temperature with an increase in the cluster size. A similar behavior has been observed for copper and gold nanoparticles. A conclusion has been drawn that 200–250 atoms is presumably the limiting size of a metallic cluster, below which the initial fcc modification cannot be kept under realistic industrial conditions. The adequacy of the results is checked in the computer experiments with Lennard-Jones nanoparticles. The results for the Lennard-Jones and metallic nanoparticles have been shown to agree with each other.     

Utility of biodegradable plasmonic nanoclusters in photoacoustic imaging

Plasmonic metal nanoparticles are used in photoacoustic imaging as contrast agents because of their resonant optical absorption properties in the visible and near-IR regions. However, the nanoparticles could accumulate and result in long-term toxicity in vivo, because they are generally not biodegradable. Recently, biodegradable plasmonic gold nanoclusters, consisting of sub-5 nm primary gold nanoparticles and biodegradable polymer stabilizer, were introduced. In this Letter, we demonstrate the feasibility of biodegradable nanoclusters as a photoacoustic contrast agent. We performed photoacoustic and ultrasound imaging of a tissue-mimicking phantom with inclusions containing nanoclusters at various concentrations. The results indicate that the biodegradable gold nanoclusters can be used as effective contrast agents in photoacoustic imaging.     

A study of many-body phenomena in metal nanoclusters (Au, Cu) close to their transition to the nonmetallic state

The results of a study of many-body phenomena in gold and copper nanoclusters are presented. The measured conductivity as a function of nanocluster height h was found to have a minimum at h ≈ 0.6 nm. Conductivity was local in character at nanocluster sizes l ≤ l _c ≈ 2.5 nm. Changes in core hole screening and an anomalous increase in the Anderson singularity index α in gold and copper nanoclusters could be caused by changes in permittivity from metallic (? → ∞) to nonmetallic (? ∝ l ²). The many-body phenomenon characteristics observed in the X-ray photoelectron and tunnel spectra of gold and copper nanoclusters as the size of the nanoclusters changed led us to suggest changes in the band structure of the nanoclusters and, therefore, their possible transition from the metallic to nonmetallic state.     

Ultrafast optical nonlinear properties of metal nanoparticles

The physical origin and the dynamics of the ultrafast optical nonlinear response of noble metal nanoparticles are analyzed around the surface plasmon resonance frequency using extension of the bulk metal electron kinetics and band structure models. The computed spectral and temporal responses are found to be in very good agreement with the measured ones in silver when taking into account the impact of electron excitation on both the interband absorption and electron optical scattering rate. A good reproduction of the strong excitation regime experimental results is also obtained in the case of gold, with a dominant contribution of the interband effect. Received: 4 July 2001 / Published online: 10 October 2001     

Polymer-inorganic composite with ultradisperse gadolinium particles

The objects of investigation are polystyrene-based composites with ultradisperse particles (including nanoparticles) of metallic Gd and SiO₂. The composites prepared by milling starting materials in a barrel mill at room temperature are studied by the ferromagnetic resonance method, transmission electron microscopy (TEM), and reflection X-ray diffraction (RXD). It is found that the magnetic subsystem of the composites is formed by magnetic nanoclusters, Gd crystallites 30 ± 10 nm across, which possess volume and surface magnetic anisotropy and pass into the superparamagnetic state at 210 ± 10 K. It is also found that the Landau-Lifshitz equation with the damping term in the Landau-Lifshitz form provides the best quantitative fit to experimental data for the ferromagnetic resonance of superparamagnetic metal nanoparticles.     

Formation of silver nanoparticles during deposition onto viscous-fluid epoxy resin

A new method is proposed for synthesizing metallic nanoparticles in a polymer matrix. These nanoparticles are synthesized during thermal vacuum evaporation of a metal (4.8 × 10⁻⁶ g/cm²) onto the surface of viscousfluid epoxy resin (at a viscosity of 20–120 Pa s) having room temperature, which is well below the glass transition temperature of the polymer. As a result, epoxy resin layers containing silver nanoparticles in their volume form; these nanoparticles are studied by transmission electron microscopy and optical absorption spectroscopy. Various types of disperse structures formed by metallic nanoparticles in the polymer are detected. The morphology of the composite material is found to be controlled by the polymer viscosity and the metal deposition time.     

Ion implantation inducing nanovoids characterized by TEM and STEM

The evolution of nanoparticles in sequentially ion-implanted Ag and Ag/Cu into silica glasses has been studied. The doses for implantation (×10¹⁶ ions/cm²) were 5Ag, 5Ag/5Cu and 5Ag/15Cu. Ag nanoclusters have been formed in the implanted 5Ag specimen. In the implanted 5Ag/5Cu specimen, some formed nanoclusters have brighter center features. With an increase of Cu ions dose, the nanoclusters with brighter center features become prevalent. The microstructural properties of the nanoparticles are characterized by transmission electron microscopy. Scanning transmission electron microscope high-angle annular dark field and high-resolution transmission electron microscopy are also utilized to study the formed nanoparticles. The results show that nanovoids have been induced into metal nanoparticles during the ion implanting process, not the core-shell nanoparticles as other workers believed. The nanovoids can be the aggregation of vacancies induced by irradiation.     

Synthesis of low-melting-point metallic nanoparticles with an ultrasonic nanoemulsion method

A one-step, economical nanoemulsion method has been introduced to synthesize low-melting-point metallic nanoparticles. This nanoemulsion technique exploits the extremely high shear rates generated by the ultrasonic agitation and the relatively large viscosity of the continuous phase - polyalphaolefin (PAO), to rupture the molten metal down to diameter below 100 nm. Field’s metal nanoparticles and Indium nanoparticles of respective average diameters of 15 nm and 30 nm have been obtained. The nanoparticles size and shape are determined by transmission electron microscopy (TEM). Their phase transition behavior is examined using a differential scanning calorimeter (DSC). It is found that these nanoparticles dispersed in PAO can undergo reversible, melting-freezing phase transition, and exhibit a relatively large hysteresis. The experimental results suggest that the nanoemulsion method is a viable route for mass production of low-melting nanoparticles.     

Metal nanocluster formation in silica films prepared by rf-sputtering: an experimental study

Composite silica films containing metal nanoclusters were prepared by the rf- sputtering technique, in which SiO₂ was co-deposited with gold+copper, gold+silver, or copper+silver. The formation of either pure or alloy clusters was studied by extended X-ray absorption fine structure spectroscopy and transmission electron microscopy. For all systems, the presence of alloy aggregates was evidenced. Moreover, small amounts of pure metal aggregates as well as dispersed or oxidized dopants were observed. 61.46.+w Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals – 61.10.Ht X-ray absorption spectroscopy: EXAFS, NEXAFS, XANES, etc. – 81.05.Pj Glass-based composites, vitroceramics Received 29 June 2001