咔唑分子拉曼激发虚态的相关研究

根据键极化率与拉曼峰强之间的关系,得到咔唑分子拉曼激发虚态随时间演化的键极化率. 将得到的键极化率的末态与用密度泛函理论得到的基态键电荷密度进行了对比,讨论并分析了拉曼激发虚态键极化率随时间弛豫的特征. 研究表明:咔唑分子在拉曼激发初态时,电子由两个骨架六元环向连通两六元环的连通键上流动,而并非向外围的C–H键上流动. 拉曼激发末态键极化率分布趋势与基态键电荷密度分布很相似,说明激发的电子又流回到分子骨架,即弛豫到基态. 通过对拉曼激发虚态键极化率弛豫过程特征时间的研究,发现连通两六元环的C–C键以及靠近连通键的C–C键的键极化率的弛豫时间较其他键的极化率弛豫时间都长,进一步说明了拉曼激发虚态电子弛豫特征. 这些结果反映了咔唑这类具有连通键的多元环分子在拉曼激发虚态所具有的特征与性质,这对拉曼激发虚态的研究有重要意义. 关键词： 拉曼峰强 键极化率 拉曼激发虚态     

甲基紫分子拉曼激发虚态的研究

从拉曼峰强入手,求得了甲基紫分子的“时间分辨键极化率”,并与第一原理计算的基态电子密度做对比,讨论了该分子的激发拉曼虚态的性质.研究结果表明,该分子的拉曼激发虚态中电子向分子外围以及两环之间的键流动,并且拉曼弛豫后的键极化率分布与基态电子的密度分布相似.通过研究键极化率的弛豫过程,发现连接两环的键上的键极化率弛豫时间较其他键大.这些结果说明了甲基紫这类双环分子拉曼激发虚态的性质,这对于研究拉曼散射的中间态具有一定意义. 关键词： 拉曼峰强 时间分辨键极化率 弛豫特征时间     

亚乙基硫脲的表面增强拉曼极化率研究：电磁和电荷转移机制

测量了吸附在银电极表面的亚乙基硫脲分子在不同电位下的表面增强拉曼光谱，对光谱强度变化进行了分析.从拉曼光谱强度计算出分子的键极化率数值，分析极化率大小和变化情况，提出了分子在不同电位下表面增强效应的增强机制. 关键词： 亚乙基硫脲 表面增强拉曼极化率 电磁增强 电荷转移增强     

亚乙基硫脲分子键伸缩模式与全耦合模式键极化率的对比及其拉曼激发虚态的相关研究

从拉曼峰强着手,得到了键伸缩模式与全耦合模式两种不同计算条件下,亚乙基硫脲(ethylene thiourea,ETU)分子的键极化率,并比较分析了两种计算结果的异同.研究表明:在键伸缩模式的算法中,仅考虑势能分布中键对称伸缩比重相对较大的部分拉曼峰参与极化率计算,显然忽略了键伸缩与键弯曲间的相互耦合,造成了与弯曲振动耦合较强的部分键伸缩极化率值存在一定误差.因此,此方法虽能使问题简化,但却丢失了一些信息.而全耦合模式算法考虑了所有振动模式(键伸缩与键弯曲)相互影响的情况,能更全面的反映键电荷的分布情况,但却会使问题的求解过程变得复杂.同时,在拉曼激发虚态的相关研究中,两种计算方法却得到几乎一致的键极化率弛豫方式(呈单指数规律衰减)及相同的衰减特征时间.     

手性分子反-2,3-环氧丁烷的旋光拉曼光谱研究

本文从拉曼峰强出发,求得了反-2,3-环氧丁烷分子的拉曼键极化率,明确了拉曼激发下电荷的分布的信息.还从旋光拉曼(Raman optical activity,ROA)谱的峰强,求取了该分子的旋光拉曼键极化率.由分子手性中心的C-H产生的偶极矩与拉曼激发过程中,电荷流动产生的跃迁磁偶极矩的耦合,来理解旋光拉曼活性产生的机理.分析表明,旋光拉曼活性分子手性中心的C-H键两侧的旋光拉曼极化率符号相反,显示着手性分子局域的不对称性.还得到了对称和反对称坐标的键极化率和旋光拉曼极化率,并且从对称性的角度,即C2群的不可约表示,讨论了这些极化率的内涵.     

哒嗪分子表面增强拉曼效应下键极化率的研究:吸附构型与增强机理

本文用拉曼峰强求得时间分辨键极化率的方法,分析了哒嗪分子在银电极上的表面增强拉曼谱图.哒嗪分子在不同电位下的键极化率和其弛豫特征时间,显示该分子的吸附点为两个氮原子,以及该分子体系的电荷转移机制机理,包括共轭的效应.对于具有良好拉曼谱图的体系,这个方法具有普适性. 关键词： 哒嗪 拉曼峰强 时间分辨键极化率 弛豫特征时间     

手性分子2, 3-丁二醇的旋光拉曼光谱研究

本文从拉曼峰和旋光拉曼峰出发,通过键极化率和微分键极化率分析研究(2R, 3R)-2, 3-丁二醇. 通过分子C₁和C₂两种点群的优化结构,获得不依赖于这两种结构的结果 和有关这个手性系统物理图像的丰富信息.对分子拉曼键极化率分析,得出在拉曼弛豫过程中, 电荷主要从外围流向骨架结构.对分子微分键极化率的分析,显示在不对称C原子和与其相联系的H原子 两侧化学键, C-O和C-CH₃的微分键极化率的符号正好相反,意味着这个分子具有相当好的手性 不对称性质.对比对称和反对称的键极化率、微分键极化率,本文得到这样的结论: 对于(特别是键伸缩的)键极化率,(大体上是)对称的大于反对称的; 而对于微分键极化率则是反对称的大于对称的. 关键词： 旋光拉曼 键极化率 微分键极化率 2,3-丁二醇     

碳纳米管拉曼光谱研究新进展

本文介绍碳纳米管拉曼光谱研究的最新进展。重点介绍金属性和半导体性碳纳米管的共振拉曼效应、表面增强拉曼效应和偏振拉曼效应。同时也介绍了碳纳米管的温度效应、压力效应和杨氏模量的拉曼光谱研究     

单分子水平罗丹明B吸附在银胶颗粒上的表面增强拉曼散射光谱研究(英文)

本文研究了单分子水平上银胶纳米体系中罗丹明B和罗丹明6G的拉曼光谱,研究结果显示单分子水平上罗丹明B的拉曼光谱作为探测试剂将可能提供更加丰富的分子信息。     

时间分辨表面增强拉曼光谱研究银电极表面硫脲和ClO_4~-共吸附层的结构

本文应用时间分辨表面增强拉曼光谱（ＴＲＳＥＲＳ）结合电位阶跃和电位扫描的方法，研究了硫脲和ＣｌＯ－４在Ａｇ电极表面的共吸附层结构。结果表明ＳＥＲＳ谱峰强度随电极电位的响应速率与电位阶跃扫描的方向有关，ＴＵ和ＣｌＯ－４在Ａｇ表面的共吸附层在不同的电位下存在两种不同的构型，并且两种构型之间转化的难易程度不同。     

The relaxations of temporal bond polarizabilities of methylviologen adsorbed on the Ag electrode by 514.5 nm excitation: a Raman intensity study

An algorithm to elucidate the temporal bond polarizabilities from the surface enhanced Raman (SERS) intensities was employed to the case of methylviologen (MV) adsorbed on the Ag electrode. This enables us to obtain the properties of its SERS mechanisms and the effect of its adsorption. The analysis shows that the charge transfer and electromagnetic mechanisms involving in this MV SERS system possess different relaxation times for its various temporal bond polarizabilities. The physics is that the process involved in the charge transfer mechanism will take longer time than that involved in the electromagnetic mechanism since it needs more time to redistribute the charges during relaxation. The time division between these two mechanisms is figured out to be around 3 ps for this system. Adsorption also enhances the relaxation of the temporal bond polarizabilities, in general. The adsorption effect is indicated by the temporal bond polarizabilities close to the final stage of relaxation. They are, in fact, the quantities parallel to the bond electronic densities in the molecular orbital (MO) concept. For comparison, the case of MV solid was also analyzed. Copyright © 2008 John Wiley & Sons, Ltd.     

The evaluation of temporal electronic structures of nonresonant Raman excited virtual state of thiourea

An algorithm has been introduced to calculate molecular bond polarizabilities of thiourea, which supply essential electronic information about the nonresonant Raman excited virtual states. The main dynamical behaviour of the excited virtual states of thiourea is that the Raman excited electrons tend to flow to the N-H bonds and C-N bonds from the S-C bonds because of the electronic repulsion effect. The difference in Raman excited electron relaxation time of thiourea under 514.5-nm and 325-nm excitations has been observed, which quantitatively shows that the Raman scattering process is dependent on the wavelength of the pumping laser. Finally, the distribution of the electrons at the final stage of relaxation is given out through the comparison between the bond electronic densities of the ground states and the bond polarizabilities after deexcitation.     

Temporal electronic structures of nonresonant Raman excited virtual states: a case study of ethylene thiourea

An algorithm is employed to elucidate molecular bond polarizabilities of ethylene thiourea including their temporal relaxation from Raman intensities, which provide much information concerning the electronic distribution of nonresonant Raman excited virtual states. The main character of the excited states of ethylene thiourea is that the excited electrons tend to flow to the molecular periphery because of electronic repulsion. It is noted that the bond electronic densities of the ground state can be mapped out by the bond polarizabilities at the final stage of relaxation. The relaxation time is shown to be proportional to the wavelength of the exciting light in agreement with Heisenberg's uncertainty principle, showing that the excitations are indeed not the stationary eigenstates. Copyright © 2007 John Wiley & Sons, Ltd.     

1,4-苯二硫醇的表面增强拉曼光谱和激发态的密度泛函理论研究

利用密度泛函理论(density functional theory,DFT)在B3LYP/6-311+g(d)(C,H,S)和Lanl2dz(Ag、Au)基组下对1,4-苯二硫醇分子及其复合物进行了结构优化和频率计算,得到了分子及其复合物稳定的化学构型和拉曼光谱。优化后的1,4-苯二硫醇分子的S—H键和苯环所在平面夹角为20.2°,分子非平面结构。模拟了金银团簇在苯硫醇分子表面的吸附行为,得到了金团簇和银团簇在分子表面的吸附方式,即,金团簇以接近平行的方向吸附于苯硫酚分子的表面而银团簇则以几乎垂直的方向吸附于分子表面。此外,还分析了静态极化率数值变化和自然键轨道(natural bond orbital,NBO)布局分析得到的电荷分布对拉曼光谱的强度变化的影响。复合物1,4-BDT-Au2,1,4-BDT-Ag2和三明治结构的Ag2-1,4-BDT-Au2拉曼光谱谱峰强度与静态极化率数值变化有很好的吻合。采用含时密度泛函理论(time dependent density functional theory,TDDFT)对Ag2-1,4-BDT-Au2复合物进行了激发态的分析计算,通过模拟吸收光谱和计算轨道跃迁单激发态,分析计算了三明治结构的电荷转移激发态,利用可视化的电荷转移,研究了表面增强拉曼(surface enhanced Raman scattering,SERS)化学增强机理。     

Temporal electronic structure of non-resonant Raman excited virtual state of P-nitroaniline by 514 nm excitation via bond polarisabilities

We have studied the temporal bond polarisabilities of para-nitroaniline from the Raman intensities by the algorithm proposed by Wu et al.in 1987 (Tian B,Wu G,Liu G 1987 J.Chem.Phys.87 7300).The bond polarisabilities provide much information concerning the electronic structure of the non-resonant Raman excited virtual state.At the initial moment by the 514.5 nm excitation,the tendency of the excited electrons (mapped out by the bond polarisabilities) is to spread to the molecular periphery,and the electronic structure of the Raman virtual state is close to the pseudo-quinonoidic state.When the final stage of relaxation is approached,the bond polarisabilities of those peripheral bonds relax faster than those closer to the molecular core,the phenyl ring.The molecule is in the benzenoidic form as demonstrated by the bond polarisabilities after relaxation.     

Study of Raman spectrum of uranium using a surface‐enhanced Raman scattering technique

Raman spectroscopic investigation on weak scatterers such as metals is a challenging scientific problem. Technologically important actinide metals such as uranium and plutonium have not been investigated using Raman spectroscopy possibly due to poor signal intensities. We report the first Raman spectrum of uranium metal using a surface‐enhanced Raman scattering‐like geometry where a thin gold overlayer is deposited on uranium. Raman spectra are detected from the pits and scratches on the sample and not from the smooth polished surface. The 514.5‐ and 785‐nm laser excitations resulted in the Raman spectra of uranium metal whereas 325‐nm excitation did not give rise to such spectra. Temperature dependence of the B_3g mode at 126 cm⁻¹ is also investigated. Copyright © 2011 John Wiley & Sons, Ltd.