Recent advances in linear and non‐linear Raman spectroscopy. Part IX

This annual review is published to provide an overview of advances in the field of Raman spectroscopy as reflected in papers published each year in the Journal of Raman Spectroscopy (JRS) as well as in trends across related journals that have published papers in the broad field of Raman spectroscopy. The content is obtained from statistical data on article counts obtained from Thomson Reuters ISI Web of Science Core Collection by year and by subfield of Raman spectroscopy. Additional information is gleaned from presentations at the VIII International Conference on Advanced Vibrational Spectroscopy (ICAVS‐8) in Vienna, Austria in July 2015 and those featuring Raman scattering at SCIX 2015 organized by the Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) in Providence, Rhode Island, USA, in September/October 2015. Coverage is also provided for topics from the conference ECONOS 2015 held in April in Leuven, Belgium. Finally, papers published in JRS in 2014 are highlighted and arranged by topics at the frontier of Raman spectroscopy. Taken from these various viewpoints, it is clear that Raman spectroscopy continues to be a rapidly expanding field that provides sensitive photonic information of matter at the molecular level in an ever‐widening arena of novel applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopic characterization of a thiophene‐based active material for resistive organic nonvolatile memories

A combined theoretical and experimental Raman study is presented on a diphenyl bithiophene molecule known as a good candidate for the development of organic nonvolatile memory devices. Spectroscopic markers suitable to distinguish the different stable conformers of the molecule have been predicted and detected. The combined analysis of theoretical and experimental Raman spectra recorded in solution indicates that at room temperature a dynamical equilibrium, characterized by interconversion between the two more stable conformers (namely trans and cis), takes place and that the more populated species is the cis form. Referring to the solid phase instead, Raman spectra of single‐crystal samples show the presence of the only trans conformer, as confirmed by X‐ray measurements. Finally, Raman spectra of thin films, as those used for the memory device, were collected; samples just deposited from solution and after few hours from the deposition were analyzed. Following the evolution of selective spectroscopic Raman markers, an isomerization process from the abundant cis (as‐deposited) to the totally trans (after few hours) conformer in the solid phase was detected. These results open the way to the identification of the molecular isomers present in the thin film of the memory cell and finally of the active molecular species involved in the switching mechanism of the operating device. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman tensor analysis of hexagonal polyoxymethylene and its application to study the molecular arrangement in highly crystalline electrospun nanofibers

The orientation dependence in space of Raman‐active vibrations in the hexagonal structure of polyoxymethylene (POM) is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. The variation of polarized intensity for the A₁ and the E₁ vibrational modes with respect to the POM molecular orientation is systematically studied, from both theoretical and experimental viewpoints, according to the symmetry assignments of each vibrational mode. A set of working equations including the Raman selection rules associated with the A₁ and the E₁ modes and the orientation distribution function are explicitly formulated and validated by means of a least‐square fitting procedure on experimental data. In addition, an approach based on the introduction of orientation distribution functions is applied to quantitatively assess and compare on a statistical base the molecular orientation of two different types of electrospun POM nanofibers. Copyright © 2012 John Wiley & Sons, Ltd.     

Measurement of the absolute Raman scattering cross sections of sulfur and the standoff Raman detection of a 6‐mm‐thick sulfur specimen at 1500 m

The absolute Raman scattering cross sections (σ_RS) for the 471, 217, and 153 cm⁻¹ modes of sulfur were measured as 6.0 ± 1.2 × 10⁻²⁷, 7.7 ± 1.6 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁶ cm² at 815, 799, and 794 nm, respectively, using a 785‐nm pump laser. The corresponding values of σ_RS at 1120, 1089, and 1081 nm were determined to be 1.5 ± 0.3 × 10⁻²⁷, 1.2 ± 0.24 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁷ cm² using a 1064‐nm laser. A temperature‐controlled, small‐cavity (2.125 mm diameter) blackbody source was used to calibrate the signal output of the Raman spectrometers for these measurements. Standoff Raman detection of a 6‐mm‐thick sulfur specimen located at 1500 m from the pump laser and the Raman spectrometer was made using a 1.4‐W, CW, 785‐nm pump laser. Copyright © 2010 John Wiley & Sons, Ltd.     

远距离探测拉曼光谱特性

为了发展远距离探测未知或危险物质的方法, 设计并建立了近同轴可见光远距离拉曼光谱探测实验装置, 对硝酸盐固体样品进行了距离为2-10 m的拉曼光谱测量, 初步研究了拉曼信号强度与激发光功率、探测距离、样品浓度及样品表面方向之间的关系. 实验观察到三种硝酸盐在1050 cm^-1附近的拉曼谱线, 其微小的差异可作为识别特征. 硝酸铵的特征拉曼谱线强度正比于激发光功率, 近似平方关系; 与探测距离之间趋向于二次反比关系; 与样品浓度接近指数关系; 与样品表面朝向有近似余弦函数的关系.     

Raman spectra and simulation of cis‐ and trans‐cyclooctene for conformational analysis compared to inelastic neutron scattering

Simulated and measured Raman spectra are used to determine the molecular conformation of trans ‐cyclooctene. This is the first reported Raman spectrum of this highly strained species. A crown structure results in a computed Raman spectrum, which is in good agreement with the experiment; a chair structure does not. Comparison is made with the case of cis ‐cyclooctene. The computed structure and limitations of the method of conformational analysis are discussed. In particular, the relative merits of Raman spectroscopy in comparison with infrared and inelastic neutron scattering (INS) are evaluated using computed spectra for all three methods and comparison of the observed INS for cis ‐cyclooctene with that computed for two conformations. It is concluded that the combination of computed and observed Raman spectra provides a useful method for conformational analysis for cases of this type. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature measurements in condensed phases using non‐resonant femtosecond stimulated Raman scattering

We have previously demonstrated the capability of femtosecond stimulated Raman scattering (FSRS) data to measure the temperature (T) of condensed matter at the molecular vibrational level. [Phys. Rev. Lett. 2011, 107, 43001] In this paper, we expand the theory for the FSRS temperature dependence by considering the effects of an isolated change of T as well as a coupled change of T and chemical concentration. We point out that the origin of the temperature sensitivity of the Stokes to anti‐Stokes ratio of FSRS lies in the exponential nonlinearity of the gain and loss. We establish that FSRS of two Raman modes can be used to simultaneously determine the vibrational temperature and the change in concentration of the species contributing to those two modes. Single‐shot experimental results using FSRS are presented to demonstrate over four orders of magnitude higher efficiency than spontaneous Raman in small volume samples with picosecond resolution. Copyright © 2012 John Wiley & Sons, Ltd.     

Morphology of InN nanorods using spectroscopic Raman imaging

We report the vibrational properties of vertical and oblique InN nanorods (NRs) grown by molecular beam epitaxy (MBE). Surface optical (SO) Raman mode at 561 cm⁻¹, belonging to E₁ symmetry [SO(E₁)], is identified along with symmetry allowed Raman modes of E₂(low), E₂(high), and E₁(LO) at 87, 489, and 589 cm⁻¹, respectively, corresponding to wurtzite InN phase. Usually, SO phonon modes arise due to breakdown of translational symmetry of surface potential at surface defects, which are attributed by the surface roughness. Intensity distribution of E₁(LO) and SO(E₁) phonon modes over a specified area have been analysed using Raman area mapping with an optical resolution of 400 nm. Imaging with E₁(LO) phonon mode, originating from the bulk of the sample, distinguishes the vertical NRs alone. We are able to resolve NR morphologies in both vertical and oblique cases with additional Raman mapping analysis of SO(E₁) phonon mode, emerging from the surface irregularities, which are confined to the tip of MBE grown NRs. Copyright © 2013 John Wiley & Sons, Ltd.     

Recent advances in linear and nonlinear Raman spectroscopy. Part VII

The aim of this paper is to provide an overview of advances in the field of Raman spectroscopy as reflected in articles published each year in the Journal of Raman Spectroscopy as well as in trends across related journals publishing in this research area. The context for this review is derived from statistical data on article counts obtained from Thomson Reuters ISI Web of Knowledge by year and by subfield of Raman spectroscopy. Additional information is gleaned from presentations featuring Raman spectroscopy presented at the International Conference on Advanced Vibrational Spectroscopy in Kobe Japan in August 2013 and at SCIX 2013 sponsored by the Federation of Analytical Chemistry and Spectroscopy Societies in Milwaukee, Wisconsin, USA, October 2013. Papers published in the Journal of Raman Spectroscopy in 2012 are highlighted in this review and reflect topics and advances at the frontier of Raman spectroscopy, a field that is expanding rapidly as a sensitive photonic probe of matter at the molecular level in an ever widening sphere of novel applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Raman polarization analysis of highly crystalline polyethylene fiber

The complex orientation dependence in space of Raman active vibrations in the orthorhombic structure of polyethylene (PE) is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. Building upon the symmetry assignment of these vibrational modes, we systematically studied, from both theoretical and experimental viewpoints, the changes of polarized intensity for the A_g and the B_2g + B_3g vibrational modes with respect to PE molecular orientation. After explicitly expanding the Raman selection rules associated with the A_g and the B_2g + B_3g modes, introducing them into general expressions of the orientation distribution function, and validating them by means of a least‐square fitting procedure on experimental data, we compare here two mesostructural models for a highly crystallized and self‐aligned PE fiber structure. Stereological arguments are shown concerning the arrangement of orthorhombic fibrils in such a sample that unfold the correct values of five independent Raman tensor elements for orthorhombic PE. Copyright © 2010 John Wiley & Sons, Ltd.     

Visible,near‐infrared,and ultraviolet laser‐excited Raman spectroscopy of the monocytes/macrophages (U937) cells

Raman spectra of the monocytes were recorded with laser excitation at 532, 785, 830, and 244 nm. The measurements of the Raman spectra of monocytes excited with visible, near‐infrared (NIR), and ultraviolet (UV) lasers lad to the following conclusions. (1) The Raman peak pattern of the monocytes can be easily distinguished from those of HeLa and yeast cells; (2) Positions of the Raman peaks of the dried cell are in coincidence with those of the monocytes in a culture cell media. However, the relative intensities of the peaks are changed: the peak centered around 1045 cm⁻¹ is strongly intensified. (3) Raman spectra of the dead monocytes are similar to those of living cells with only one exception: the Raman peak centered around 1004 cm⁻¹ associated with breathing mode of phenylalanine is strongly intensified. The Raman spectra of monocytes excited with 244‐nm UV laser were measured on cells in a cell culture medium. A peak centered at 1485 cm⁻¹ dominates the UV Raman spectra of monocytes. The ratio I₁₅₇₄/I₁₆₁₃ for monocytes is found to be around 0.71. This number reflects the ratio between proteins and DNA content inside a cell and it is found to be twice as high as that of E. coli and 5 times as high as that of gram‐positive bacteria. Copyright © 2009 John Wiley & Sons, Ltd.     

Recent advances in linear and nonlinear Raman spectroscopy. Part IV

The purpose of the review is to provide a concise overview of recent advances in the broadly defined field of Raman spectroscopy as reflected in part by the many articles published each year in the Journal of Raman Spectroscopy (JRS) as well as in trends across all related journals publishing in this research area. Context for the review is provided by considering statistical data on citations for the Thompson Reuters ISI Web of Science by year and by subfield of Raman spectroscopy. Additional statistics of number of papers and posters presented by category at the XXII International Conference on Raman Spectroscopy (ICORS 2010) is also provided. Papers published in JRS in 2009, as reviewed here, reflect trends at the cutting edge of Raman spectroscopy which is expanding rapidly as a sensitive photonic probe of matter at the molecular level with an ever widening sphere of novel applications. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Raman scattering of MnOx?CeOx composite catalysts: structural aspects and laser‐heating effects

Composite MnO_x CeO_x catalysts (Mn_at: Ce_at = 1) synthesized via the redox and coprecipitation routes were comparatively characterized by micro‐Raman spectroscopy using a laser irradiation power ranging between 0.6 and 4.2 mW. A quasi‐molecular dispersion of the oxide species determines a major and irreversible structural rearrangement of the redox MnO_x CeO_x system because of severe heating effects for laser power in excess of 0.6 mW. The X‐ray diffraction data of samples calcined in the range of 673 1273 K confirm that the micro‐Raman characterization of the composite MnO_x CeO_x systems requires an adequate minimization of the irradiation power to prevent the strong sintering and restructuring phenomena due to laser‐heating effects. Copyright © 2011 John Wiley & Sons, Ltd.     

Towards a rational drug design: Raman micro‐spectroscopy analysis of prostate cancer cells treated with an aqueous extract of Nerium Oleander

Raman spectroscopy is an efficient optical technique used to identify and grade cancer on the basis of the molecular composition of the cell. In this work Raman spectroscopy is used to study the chemical alteration occurring inside a prostate cancer cell as a result of a treatment with a low‐concentration aqueous extract of Nerium Oleander. The results show that Nerium Oleander affects the protein and lipid concentration of cancer cells. Copyright © 2009 John Wiley & Sons, Ltd.     

High‐resolution stimulated Raman study of the first vibrational hot band of 14N2. Separate observation of the spectra of the ortho and para species.

We present high‐resolution stimulated Raman spectra of the first hot band of nitrogen, ¹⁴N₂, obtained under conditions of low sample pressure and temperature. The use of a Raman optical pumping system allowed us to transfer a significant amount of population to the v = 1 vibrational state, which made possible the observation of the aforementioned hot band with good S/N ratio without resorting to the use of high temperatures or pressures. This has resulted in a more precise and accurate determination of the peak positions than previously existing ones, which in turn has yielded improved values for the molecular constants obtained from the analysis. The rotational selectivity of the pumping process (only one rotational state is initially populated in v = 1), coupled with the negligible probability of nuclear spin interconversion in the time frame of the experiment, has allowed us to observe the hot band spectra of the ortho and para species of ¹⁴N₂ separately. Copyright © 2013 John Wiley & Sons, Ltd.     

Vibrational Spectroscopic Characterization of the Sulphate-Carbonate Mineral Burkeite: Implications for Evaporites

Burkeite formation is important in saline evaporites and in pipe scales. Burkeite is an anhydrous sulphate-carbonate with an apparent variable anion ratio. Such a formula with two oxyanions lends itself to vibrational spectroscopy. Two symmetric sulphate stretching modes are observed, indicating at least at the molecular level the nonequivalence of the sulphate ions in the burkeite structure. The strong Raman band at 1065 cm^?1 is assigned to the carbonate symmetric stretching vibration. The series of Raman bands at 622, 635, 645, and 704 cm^?1 are assigned to the ν₄ sulphate bending modes. The observation of multiple bands supports the concept of a reduction in symmetry of the sulphate anion from T _d to C _3v or even C _2v.     

Optical properties of Stranski–Krastanov grown three-dimensional Si/Si1−xGex nanostructures

Detailed Raman and photoluminescence (PL) measurements are reported for Si/Si_1−xGe_x nanostructures grown by molecular beam epitaxy under near Stranski–Krastanov (S–K) growth mode conditions. In samples with x ranging from 0.096 to 0.53, we observe that an increase in the Raman signal related to Ge–Ge vibrations correlates with (i) a red shift in the PL peak position, (ii) an increase in the activation energy of PL thermal quenching, and (iii) an increase in the PL quantum efficiency. The results indicate that for x>0.5 Ge atoms form nanometer size clusters with a nearly pure Ge core surrounded by a SiGe shell. Time-resolved PL measurements reveal a stretched-exponential long-lived PL component that is associated with compositional and dimensional fluctuations in the SiGe dots.     

Vibrational spectroscopy of tolane; Coriolis coupling between Raman-active modes of g symmetry

ABSTRACT

Vibrational spectroscopy of tolane (diphenylacetylene), which has 66 normal modes, has been advanced. Anharmonic wavenumber predictions were made with the quartic potential energy surface obtained with B3LYP/cc-pVTZ model and the second-order perturbation theory (VPT2). Infrared (IR) intensity and Raman activities were computed at the harmonic level. The IR spectrum of the crystal and Raman spectra of the liquid and the crystal tolane were newly recorded. The lingering problem of an excess of polarised Raman bands at wavenumbers appropriate for fundamentals, other than a_g modes, has now been attributed to Coriolis coupling within modes of g symmetry species. Consequently, D_2h point symmetry group has been confirmed for a planar tolane molecule. Assignments for almost all fundamentals of tolane are now secure. The assignment for ν₃₂ remains questionable. Remaining unassigned fundamentals are: ν₃₄ and ν₃₅, which, as a_u symmetry species, are IR- and Raman-inactive transitions, and ν₅₉(b_2u), which is predicted to have a very low wavenumber.