The destruction-free analysis of polymers by fourier transform infrared photoacoustic and fourier transform Raman spectroscopy: A comparison

With the introduction of rapid–scanning Fourier transform infrared (FTIR) and recently Raman (FT–Raman) spectroscopy, vibrational spectroscopy has been launched into a new era of applications in polymer chemistry and physics. Thus, the increase in sensitivity provided by multiple scanning has led to the breakthrough of new, destruction–free sampling techniques, such as photoacoustic and Raman spectroscopy. This paper provides a comparison between data produced by FTIR photoacoustic and FT–Raman analysis of a range of polymers, and structural information available from both techniques is discussed.     

Vibrationally selective radiative and non-radiative transitions in gaseous hydrogen molecules

An efficient vibrationally selective technique to build-up the v″=1 vibrational levels in gaseous hydrogen is demonstrated using stimulated Raman pumping (SRP). Both photo-acoustic Raman spectroscopy (PARS) and coherent anti-Stokes Raman spectroscopy (CARS) are used to study non-radiative and radiative (v″=0 and v″=1) transitions in gaseous H(2) molecules. The population fraction in the v″=1 vibrational level has been estimated using combined photo-acoustic and coherent anti-Stokes Raman spectroscopy with stimulated Raman pumping.     

High-pressure vibrational spectroscopy of energetic materials: hexahydro-1,3,5-trinitro-1,3,5-triazine

Vibrational spectroscopy has been used to investigate the room-temperature high-pressure phases of the energetic material hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The pressure-induced alterations in the spectral profiles were studied in a compression sequence to 30.2 GPa using Raman spectroscopy and to 26.6 GPa using far-infrared spectroscopy. At pressures near 4.0 GPa, several changes become immediately apparent in the Raman spectrum, such as large frequency shifts, mode splittings, and intensity changes, which are associated with a phase transition from alpha-RDX to gamma-RDX. Our study extends the kinetic stability of gamma-RDX to pressures near 18.0 GPa. Evidence for a new phase was found at pressures between 17.8 and 18.8 GPa and is based on the appearance of new vibrational bands and associated changes in intensity patterns. The new phase has vibrational characteristics that are similar to those of beta-RDX, suggesting the two polymorphs share a related crystal structure.     

Vibrational spectroscopy: a 'vanishing' discipline?

The aim of this tutorial review is to convince a broad readership that vibrational spectroscopy, although according to some vibrational spectroscopists seemingly less in focus nowadays than in days past, is far from 'dead'. It may seem to some that infrared and Raman spectroscopy are less in focus than in times past, despite the unique analytical capabilities. Vibrational spectroscopy is particularly powerful for non-destructive characterisation of substances, including living material. But compared to the past, a shift in applications has taken place, bringing new opportunities. This is partly due to the introduction of new features, including imaging and 2D correlation spectroscopy. Another factor is the recognition that vibrational spectroscopy can play a role in new rather than only in the traditional fields of application, e.g. new applications in the life-science field (living cells, cancer research), the characterisation of soil. But also the traditional application in catalysis sees new development within the context of Operando spectroscopy.     

C-H stretching vibrations of methyl, methylene and methine groups at the vapor/alcohol (N = 1-8) interfaces

In IR and Raman spectral studies, the congestion of the vibrational modes in the C-H stretching region between 2800 and 3000 cm(-1) has complicated spectral assignment, conformational analysis, and structural and dynamics studies, even with quite a few of the simplest molecules. To resolve these issues, polarized spectra measurement on a well aligned sample is generally required. Because the liquid interface is generally ordered and molecularly thin, and sum frequency generation vibrational spectroscopy (SFG-VS) is an intrinsically coherent polarization spectroscopy, SFG-VS can be used for discerning details in vibrational spectra of the interfacial molecules. Here we show that, from systematic molecular symmetry and SFG-VS polarization analysis, a set of polarization selection rules could be developed for explicit assignment of the SFG vibrational spectra of the C-H stretching modes. These polarization selection rules helped assignment of the SFG-VS spectra of vapor/alcohol (n = 1-8) interfaces with unprecedented details. Previous approach on assignment of these spectra relied on IR and Raman spectral assignment, and they were not able to give such detailed assignment of the SFG vibrational spectra. Sometimes inappropriate assignment was made, and consequently misleading conclusions on interfacial structure, conformation and even dynamics were reached. With these polarization rules in addition to knowledge from IR and Raman studies, new structural information and understanding of the molecular interactions at these interfaces were obtained, and some new spectral features for the C-H stretching modes were also identified. Generally speaking, these new features can be applied to IR and Raman spectroscopic studies in the condensed phase. Therefore, the advancement on vibrational spectra assignment may find broad applications in the related fields using IR and Raman as vibrational spectroscopic tools.     

Visualization of Vibrational Modes in Real Space by Tip‐Enhanced Non‐Resonant Raman Spectroscopy

We present a general theory to model the spatially resolved non‐resonant Raman images of molecules. It is predicted that the vibrational motions of different Raman modes can be fully visualized in real space by tip‐enhanced non‐resonant Raman scattering. As an example, the non‐resonant Raman images of water clusters were simulated by combining the new theory and first‐principles calculations. Each individual normal mode gives rise its own distinct Raman image, which resembles the expected vibrational motions of the atoms very well. The characteristics of intermolecular vibrations in supermolecules could also be identified. The effects of the spatial distribution of the plasmon as well as nonlinear scattering processes were also addressed. Our study not only suggests a feasible approach to spatially visualize vibrational modes, but also provides new insights in the field of nonlinear plasmonic spectroscopy.     

Raman spectroscopy of some basic chloride containing minerals of lead and copper

Raman spectroscopy has been used to characterise several lead and mixed cationic-lead minerals including mendipite, perite, laurionite, diaboléite, boléite, pseudoboléite, chloroxiphite, and cumengéite. Raman spectroscopy enables their vibrational spectra to be compared. The low wavenumber region is characterised by the bands assigned to cation-chloride stretching and bending modes. Phosgenite is a mixed chloride-carbonate mineral and a comparison is made with the molecular structure of the aforementioned minerals. Each mineral shows different hydroxyl stretching vibrational patterns, but some similarity exists in the Raman spectra of the hydroxyl deformation modes. Raman spectroscopy lends itself to the study of these types of minerals in complex mineral systems involving secondary mineral formation.     

Kinetic and thermodynamic stability of cluster compounds under heating

A new polymorphic form of Norfloxacin has been identified and fully characterized by a variety of methods including powder X-ray diffraction, vibrational spectroscopy (IR and Raman), thermal analysis (DSC and TG), SEM and solid-state NMR spectroscopy. The relationship between the new form C and the previously known forms A and B have been studied. Moreover, the crystal structure of the known form A has been solved by single-crystal methods.     

Enhancement factor averaging and the photostability of probes in SERS vibrational pumping

The technique of temperature dependent vibrational pumping in surface enhanced Raman scattering (SERS) has been recently demonstrated as a promising new tool to estimate SERS cross-sections. In this paper we expand on the previous developments and study several details around the implementation and physics of the vibrational pumping technique in SERS. Here we concentrate on two specific aspects related to: (i) the different averaging properties (over the distribution of enhancements) of the Stokes and anti-Stokes signals in the pumping regime; and (ii) the role of the finite photostability of the probes. The fact that the anti-Stokes signal is averaged differently from the Stokes counterpart leads to some unique phenomena in Raman spectroscopy that can only be observed under the conditions of vibrational pumping in SERS.     

Vibrational population distributions in infrared multiple-photon excitation probed by coherent anti-stokes Raman spectroscopy

Coherent anti-stokes Raman spectroscopy has been used as a probe for molecules pumped by high-intensity CO₂ laser radiation. Ozone, sulfur hexafluoride, and chloroethane have been investigated. The intensity of the ground-state CARS signal is decreased by IR multiphoton excitation, but signals at new vibrational origins do not appear. The observations on chloroethane are interpreted in terms of a rate-equation model for IRMPE, modified to take vibrational redistribution into account.     

Detection of the Sulfhydryl Group in Proteins by Raman Scattering Spectroscopic Method

Detection of the sulfhydryl group in proteins has previously been difficult. However, the group can be detected quite easily by Raman spectroscopy due to its distinct vibrational band at 2560-2580 cm^?1 region. This region is free of interference from other vibrational bands of protein. Detection of SH in tobacco mosaic virus coat protein and two sea snake neurotoxins was made to illustrate the application of Raman spectroscopy.     

Inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy (IETS) is a relatively new form of vibrational spectroscopy which is able to address problems previously unsolved by either IR or Raman. It is particularly useful for surface analysis.     

Identification of a new co-crystal of salicylic acid and benzamide of pharmaceutical relevance

Raman spectroscopy, X-ray powder diffraction/X-ray crystallography and differential scanning calorimetry have been used to study the phenomenon of co-crystal formation in stoichiometric mixtures of salicylic acid with benzamide. Raman spectroscopy was particularly useful for the characterization of the products and was used to determine the nature of the interactions in the co-crystals. It was observed that little change in the vibrational modes associated with the phenyl groups of the respective reactants took place upon co-crystal formation, but changes in intensities of the vibrational modes associated with the amide and the carboxylic acid groups were observed upon co-crystal formation. Several new vibrational bands were identified in the co-crystal which were not manifested in the physical mixture of both components and could be used as diagnostic features of co-crystal formation.     

Raman under nitrogen. The high-resolution Raman spectroscopy of crystalline uranocene, thorocene, and ferrocene

The utility of recording Raman spectroscopy under liquid nitrogen, a technique we call Raman under nitrogen (RUN), is demonstrated for ferrocene, uranocene, and thorocene. Using RUN, low-temperature (liquid nitrogen cooled) Raman spectra for these compounds exhibit higher resolution than previous studies, and new vibrational features are reported. The first Raman spectra of crystalline uranocene at 77 K are reported using excitation from argon (5145 A) and krypton (6764 A) ion lasers. The spectra obtained showed bands corresponding to vibrational transitions at 212, 236, 259, 379, 753, 897, 1500, and 3042 cm(-1), assigned to ring-metal-ring stretching, ring-metal tilting, out-of-plane CCC bending, in-plane CCC bending, ring-breathing, C-H bending, CC stretching and CH stretching, respectively. The assigned vibrational bands are compared to those of uranocene in THF, (COT)2-, and thorocene. All vibrational frequencies of the ligands, except the 259 cm(-1) out-of-plane CCC bending mode, were found to increase upon coordination. A broad, polarizable band centered about approximately 460 cm(-1) was also observed. The 460 cm(-1) band is greatly enhanced relative to the vibrational Raman transitions with excitations from the krypton ion laser, which is indicative of an electronic resonance Raman process as has been shown previously. The electronic resonance Raman band is observed to split into three distinct bands at 450, 461, and 474 cm(-1) with 6764 A excitation. Relativistic density functional theory is used to provide theoretical interpretations of the measured spectra.     

Irreducible representation and projection operator application to understanding nonlinear optical phenomena: hyper-Raman, sum frequency generation, and four-wave mixing spectroscopy

Symmetry plays an essential role in understanding optical activities of a molecule in infrared and Raman vibrational spectroscopy as well as in nonlinear optical vibrational spectroscopy. Each vibrational mode belongs to an irreducible representation of the underlying symmetry group. In this paper, using the alpha-helical polypeptide symmetry as an example, we calculate all the third rank nonzero hyper-Raman tensors as well as the infrared and Raman tensors by applying the projection operators to each irreducible species. We demonstrate that the projection operator method provides selection rules for the infrared, Raman, and hyper-Raman vibrational transitions and also other nonlinear optical spectroscopy such as sum frequency generation and the four-, five-, and six-wave mixing coherent vibrational transitions. Specific expressions for all nonzero elements of the corresponding nonlinear susceptibility tensors in a laboratory-fixed coordinate frame are also deduced.     

Raman spectroscopy in the near infrared – a most capable method of vibrational spectroscopy

Raman spectroscopy has enjoyed a dramatic improvement during the last years: The interference by the fluorescence of impurities is virtually eliminated, the sample preparation is considerably easier as for infrared spectroscopy and many applications in routine analytics, quality control and process control in various branches of industry are now possible. It is shown that the up-to-date near-infrared Raman spectrometers now meet most demands for a modern analytical instrument concerning applicability, analytical information and convenience. It can be anticipated that Raman spectroscopy will catch up infrared spectroscopy, the current workhorse of vibrational spectroscopy.     

Raman spectroscopy: Recent advancements,techniques and applications

Vibrational spectroscopy has proven itself to be a valuable contributor in the study of various fields of science, primarily due to the extraordinary versatility of sampling methods. Raman measurement gives the vibrational spectrum of the analyte, which can be treated as its “fingerprint,” allows easy interpretation and identification. Over the last years, there has been tremendous technical improvement in Raman spectroscopy, as overcome by the problems like fluorescence, poor sensitivity or reproducibility. This article reviews the recent advances in Raman spectroscopy and its new trend of applications ranging from ancient archaeology to advanced nanotechnology. It includes the aspects of Raman spectroscopic measurements to the analysis of various substances categorized into distinct application areas such as biotechnology, mineralogy, environmental monitoring, food and beverages, forensic science, medical and clinical chemistry, diagnostics, pharmaceutical, material science, surface analysis, etc. Advances in the instrumental design of Raman spectrometers coupled with newly developed sampling methodologies have also been described which enable trace level detection and satisfactory analysis.