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.     

Investigation of hydrogen bonding in neat dimethyl sulfoxide and binary mixture (dimethyl sulfoxide + water) by concentration-dependent Raman study and ab initio calculation

In this study,our vibrational spectroscopic analysis is made on hydrogen-bonding between dimethyl sulfoxide and water comprises both experimental Raman spectra and ab initio calculations on structures of various dimethyl sulfoxide/water clusters with increasing water content.The Raman peak position of the v(S=O) stretching mode of dimethyl sulfoxide serves as a probe for monitoring the degree of hydrogen-bonding between dimethyl sulfoxide and water.In addition,the two vibrational modes,namely,the CH 3 symmetric stretching mode and the CH 3 asymmetric stretching mode have been analysed under different concentrations.We relate the computational results to the experimental vibrational wavenumber trends that are observed in our concentration-dependent Raman study.The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the nature of the hydrogen bonding and the structures of the hydrogen-bonded complexes studied.     

Nano‐imaging through tip‐enhanced Raman spectroscopy: Stepping beyond the classical limits

The spatial resolution in optical imaging is restricted by so‐called diffraction limit, which prevents it to be better than about half of the wavelength of the probing light. Tip‐enhanced Raman spectroscopy (TERS), which is based on the SPP‐induced plasmonic enhancement and confinement of light near a metallic nanostructure, can however, overcome this barrier and produce optical images far beyond the diffraction limit. Here in this article, the basic phenomenon involved in TERS is reviewed, and the high spatial resolution achieved in optical imaging through this technique is discussed. Further, it is shown that when TERS is combined with some other physical phenomena, the spatial resolution can be dramatically improved. Particularly, by including tip‐applied extremely localized pressure in TERS process, it has been demonstrated that a spatial resolution as high as 4 nm could be achieved.     

Al2O3薄膜/纳米Ag颗粒复合结构的光吸收谱及增强Raman散射光谱研究

Al₂O₃介质薄膜与纳米Ag颗粒构成的复合结构,被应用于表面增强Raman散射探测实验中,其中Al₂O₃介质薄膜对纳米Ag颗粒的吸收谱及增强Raman散射光谱的影响被特别关注.该复合结构的光学特性表征出纳米Ag颗粒的偶极振荡特性.从光吸收谱中可以看到,其共振吸收谱随Al₂O₃介质薄膜厚度增加而在整个谱域上发生红移,表明纳米Ag颗粒的周围介电常数随Al₂O₃介质薄膜厚度的增加而增大.采用罗丹明6G作为探针原子,6个Raman特征峰的平均增益值作为表征表面增强Raman散射衬底增益程度的量度.实验结果表明,Al₂O₃介质薄膜层的引入提高了纳米Ag颗粒的衬底介电常数,并引起了散射共振的增强,从而使表面增强Raman散射强度提高.     

Anatase—a pigment in ancient artwork or a modern usurper?

Fragments of wall-paintings from Roman villas in Easton Maudit, which date from ca 150 AD have been studied by Raman spectroscopy. An intact ancient Roman paint pot discovered in the remains of a villa in Castor, Cambridgeshire, still containing a mixture of white and red pigment was also analysed and the pigments identified as haematite and anatase. The discovery of anatase in the intact artist’s paint pot, particularly, and also on fragments of broken paint pots from the Easton Maudit villa site, is a unique contribution to current knowledge of ancient European pigment history, because the presence of this mineral has not hitherto been recognised fully in an ancient artist’s palette. The relative spectral response of anatase and haematite in the Raman data is compared with that of anatase and other red pigments such as minium, cinnabar, and litharge.     

Life in the sabkha: Raman spectroscopy of halotrophic extremophiles of relevance to planetary exploration

The Raman spectroscopic biosignatures of halotrophic cyanobacterial extremophiles from sabkha evaporitic saltpans are reported for the first time and ideas about the possible survival strategies in operation have been forthcoming. The biochemicals produced by the cyanobacteria which colonise the interfaces between large plates of clear selenitic gypsum, halite, and dolomitized calcium carbonates in the centre of the salt pans are identifiably different from those which are produced by benthic cyanobacterial mats colonising the surface of the salt pan edges in the intertidal zone. The prediction that similar geological formations would have been present on early Mars and which could now be underlying the highly peroxidised regolith on the surface of the planet has been confirmed by recent satellite observations from Mars orbit and by localised traverses by robotic surface rovers. The successful adoption of miniaturised Raman spectroscopic instrumentation as part of a scientific package for detection of extant life or biomolecular traces of extinct life on proposed future Mars missions will depend critically on interpretation of data from terrestrial Mars analogues such as sabkhas, of which the current study is an example.     

Three-Dimensional Quantum State Transferring Between Two Remote Atoms by Adiabatic Passage under Dissipation

Recently, Zhou et al. [Phys. Rev. A 79 （2009） 044304] proposed a scheme for transferring three-dimensional quantum states between remote atomic qubits confined in cavities connected by fibers through adiabatic passage. In order to avoid the decoherence due to spontaneous emission, Zhou et al. utilized the large detuning atom-field interaction. In the present paper, we discuss the influence of dissipation on the scheme in both the resonant atom-field interaction case and the large detuning case. We numerically analyze the success probability and the transferring fidelity. It is shown that the resonant case is a preferable choice for the technique of the stimulated Raman adiabatic passage （STIRAP） due to the shorter operation time and the smaller probability of dissipation.     

Use of thermo‐Raman spectroscopy and chemometric analysis to identify dehydration steps of hydrated inorganic samples—application to copper sulfate pentahydrate

In situ thermo‐Raman spectroscopy (TRS) measurements were performed in order to investigate solid‐phase transformation of the copper sulfate pentahydrate from room temperature up to 300 °C. Band‐target entropy minimization (BTEM), a blind‐source separation algorithm, was employed in order to identify and reconstruct the pure component spectra of the species involved in the dehydration process. In spite of low signal‐to‐noise ratio and elevated baseline spectral data, BTEM was successfully utilized to identify and reconstruct four pure component spectra of copper sulfate pentahydrate, trihydrate, monohydrate, and anhydrate, which were formed during this thermally induced process. Subsequent mapping of these four pure component spectral estimates back onto the preprocessed spectra yielded the relative concentrations of each individual species. Finally, the transition temperatures of each dehydration step could be unambiguously deduced from the obtained concentration profile. The current study shows that combined thermo‐Raman spectroscopy and chemometric analysis provides an effective tool to determine the dehydration temperatures as well as to identify the structures of each individual species involved in a solid‐phase dehydration process. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering and density functional theory studies of bis(4‐aminophenyl)sulfone

Raman and surface‐enhanced Raman scattering (SERS) spectra of dapsone by using colloidal silver nanoparticles have been recorded. Density functional theory was used for the optimization of ground state geometries and simulation of the vibrational spectrum of this molecule. The SERS spectrum with a large silver cluster as a model metallic surface was simulated for the first time. Taking into account the experimental and calculated Raman as well as the SERS normal modes and the corresponding assignments, along with the modeling of the free dapsone and the one in the presence of the colloidal silver nanoparticles, the importance of the sulfone group on the SERS effect in dapsone was inferred. Copyright © 2009 John Wiley & Sons, Ltd.     

A pigment (CuS) identified by micro‐Raman spectroscopy on a Chinese funerary lacquer ware of West Han Dynasty

A blue pigment was identified by micro‐Raman spectroscopy, X‐ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) and X‐ray diffraction (XRD). The test sample, a funerary lacquer tray, belongs to West Han Dynasty (206 BC–AD 8) of China and was decorated with faint blue patterns. The result from Raman spectroscopy showed that the faint blue is covellite (CuS) due to the presence of a characteristic peak at 474.5 cm⁻¹, which further was confirmed by XRF, SEM–EDX and XRD. This research indicated that CuS had been used as a blue pigment to decorate lacquer wares from the West Han Dynasty in China. Copyright © 2009 John Wiley & Sons, Ltd.