Vibrational spectroscopy introduction

Wilson, E. B. Jr, Decius, J. C. and Cross, P. C. (1980) Molecular Vibrations, Dover, New York. Woodward, L. A. (1972) Introduction to the Theory of Molecular Vibrations and Vibrational Spectroscopy, Oxford University Press, Oxford. 

M. Diem, Introduction to Modem Vibrational Spectroscopy,Johm Wiley Sons, Inc., New York, 1993. 

As this chapter aims at explaining the basics, operational principles, advantages and pitfalls of vibrational spectroscopic sensors, some topics have been simplified or omitted altogether, especially when involving abstract theoretical or complex mathematical models. The same applies to methods having no direct impact on sensor applications. For a deeper introduction into theory, instrumentation and related experimental methods, comprehensive surveys can be found in any good textbook on vibrational spectroscopy or instrumental analytical chemistry1"4. 

The book has been written as an introductory text, not as an exhaustive review. It is meant for students at the start of their Ph.D. projects and for anyone else who needs a concise introduction to catalyst characterization. Each chapter describes the physical background and principles of a technique, a few recent applications to illustrate the type of information that can be obtained, and an evaluation of possibilities and limitations. A chapter on case studies highlights a few important catalyst systems and illustrates how powerful combinations of techniques are. The appendix on the surface theory of metals and on chemical bonding at surfaces is included to provide better insight in the results of photoemission, vibrational spectroscopy and thermal desorption. 

As noted in the Introduction, a central focus of our current interests in both surface Raman and infrared spectroscopies is directed towards their utilization in reactive electrochemical systems (3-6). An important virtue of in-situ vibrational spectroscopies for this purpose is that they can yield information on the molecular identity (as well as detailed physical state) of electrogenerated species, and hence can provide considerable mechanistic information for multistep electrode processes. We have recently discussed several facets of such applications in a conference paper for "Surface Vibrations V" (6b). 

Busca, G. (1996) The use of vibrational spectroscopies in studies of heterogeneous catalysis by metal oxides an introduction. Catal. Today, 27, 323-352. 

T.L. Threlfall and J.M. Chalmers, Vibrational spectroscopy of solid-state forms - introduction, principles and overview, in Applications of Vibrational Spectroscopy in Pharmaceutical Research and Development, D.E. Pivonka, J.M. Chalmers, and RR. Griffiths (Eds), Wiley-Interscience, New York, 2007. 

A promising recent development in the study of nitrenium ions has been the introduction of time-resolved vibrational spectroscopy for their characterization. These methods are based on pulsed laser photolysis. However, they employ either time resolved IR (TRIR) or time-resolved resonance Raman (TRRR) spectroscopy as the mode of detection. While these detection techniques are inherently less sensitive than UV-vis absorption, they provide more detailed and readily interpretable spectral information. In fact, it is possible to directly calculate these spectra using relatively fast and inexpensive DFT and MP2 methods. Thus, spectra derived from experiment can be used to validate (or falsify) various computational treatments of nitrenium ion stmctures and reactivity. In contrast, UV-vis spectra do not lend themselves to detailed structural analysis and, moreover, calculating these spectra from first principles is still expensive and highly approximate. 

Diem, M., Introduction to Modern Vibrational Spectroscopy, J. Wiley Sons, New York, 1993. 

L. Woodward, Introduction to the Theory of Molecular Vibrations and Vibrational Spectroscopy, Oxford University Press, Oxford, 1976. 

The Second-Order Raman Spectrum of IJC Diamond An Introduction to Vibrational Spectroscopy of the Solid State 32... 

This appendix begins with a brief introduction to the physics of metal surfaces. We limit ourselves to those properties of surfaces that play a role in catalysis or in catalyst characterization. The second part includes an introduction to the theory of chemisorption, and is intended to serve as a theoretical background for the chapters on vibrational spectroscopy, photoemission, and the case study on promoter effects. General textbooks on the physics and chemistry of surfaces are listed in [1-8]. 

Vibrational spectroscopy is an important tool for the characterization of various chemical species. Valuable information regarding molecular structures as well as intra- and intermolecular forces can be extracted from vibrational spectral data. Recent advances, such as the introduction of laser sources to Raman spectroscopy, the commercial availability of Fourier transform infrared spectrometers, and the continuing development and application of the matrix-isolation technique to a variety of chemical systems, have greatly enhanced the utility of vibrational spectroscopy to chemists. 

M. Diem, Introduction to Modem Vibrational Spectroscopy , John Wiley Sons, New York, 1993. This easy to read book features detailed discussion of the theoretical and experimental aspects of IR and Raman spectroscopy and provides many examples for the interpretation of vibrational spectra. 

Empirical energy functions were originally developed for energy minimization and molecular dynamics studies of macromolecular structure and function (see [31], for an introduction). The parameters of the empirical potential energy Echem are inferred from experimental as well as theoretical investigations, in particular, vibrational spectroscopy and small-molecule crystallography [25-30],... 

An overview of basic physics necessary to understand neutron scattering experiments is presented below. This section is a brief introduction to vibrational spectroscopy with neutrons. More details can be found in Ref. [Lovesey 1984], Experienced readers should ignore this rather superficial introduction. 

Romeo, M.J., Dukor, R.K. and Diem, M. (2008) Introduction to spectral imaging, and applications to diagnosis of lymph nodes, in Vibrational Spectroscopy for Medical Diagnosis (eds M. Diem, P.R. Griffiths and ).M. Chalmers), John Wiley Sons, Ltd, Chichester, UK, pp. 1-26. 

Jeffrey, G. A. (1997) An Introduction to Hydrogen Bonding, Oxford University Press, New York. Hobza, P. and Havlas, Z. (2000) Blue-shifting hydrogen bonds, Chem. Rev. 100, 4253 264. Hallam, H. E. (1973) Vibrational Spectroscopy of Trapped Species, John Wiley, New York. 

With the ever-increasing need to improve quality and productivity in the analytical pharmaceutical laboratory, automation has become a key component. Automation for vibrational spectroscopy has been fairly limited. Although most software packages for vibrational spectrometers allow for the construction of macro routines for the grouping of repetitive software tasks, there is only a small number of automation routines in which sample introduction and subsequent spectral acquisition/data interpretation are available. For the routine analysis of alkali halide pellets, a number of commercially available sample wheels are used in which the wheel contains a selected number of pellets in specific locations. The wheel is then indexed to a sample disk, the IR spectrum obtained and archived, and then the wheel indexed to the next sample. This system requires that the pellets be manually pressed and placed into the wheel before automated spectral acquisition. A similar system is also available for automated liquid analysis in which samples in individual vials are pumped onto an ATR crystal and subsequently analyzed. Between samples, a cleaning solution is passed over the ATR crystal to reduce cross-contamination. Automated diffuse reflectance has also been introduced in which a tray of DR sample cups is indexed into the IR sample beam and subsequently scanned. In each of these cases, manual preparation of the sample is necessary (23). In the field of Raman spectroscopy, automation is being developed in conjunction with fiber-optic probes and accompanying... 

R. L. Carter (1998) Molecular Symmetry and Group Theory, Wiley, New York - An introduction to molecular S5mmetry and group theory as applied to chemical problems including vibrational spectroscopy. 

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