Abstract: Argon-supported inductively coupled plasmas operated at atmospheric pressures are excellent vaporization-atomization-excitation-ionization sources for analytical atomic emission spectroscopy. When a polychromator is used for observing the emitted spectra, the metals and metalloids can be determined simultaneously at the ultratrace, trace, minor, and major concentration levels under one set of experimental parameters. Alternatively, programmable scanning spectrometers may be utilized for sequential determinations. The atomization-excitation process is remarkably free of interelement interactions, the powers of detection are in the part per billion range for most elements, and sample manipulation requirements prior to analyses are often minimal. The technique meets the requirements of an analytical system for the simultaneous or sequential determination of the elements at all concentration levels to an unusual high degree.

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Abstract: PART 1. EQUILIBRIUM 1. The properties of gases 2. The first law 3. The second law 4. Physical transformations of pure substances 5. Simple mixtures 6. Phase diagrams 7. Chemical equilibrium PART 2. STRUCTURE 8. Quantum theory: introduction and principles 9. Quantum theory: techniques and applications 10. Atomic structure and atomic spectra 11. Molecular orbitals for polyatomic systems 12. Molecular symmetry 13. Spectroscopy 1: rotational and vibrational spectra 14. Spectroscopy 2: electronic transitions 15. Spectroscopy 3: magnetic resonance 16. Statistical thermodynamics: the concepts 17. Statistical thermodynamics: the machinery 18. Molecular interactions 19. Materials 1: Macromolecules and aggregates 20. Materials 2: The solid state PART 3. CHANGE 21. Molecules in motion 22. The rates of chemical reactions 23. The kinetics of complex reactions 24. Molecular reaction dynamics 25. Processes at solid surfaces DATA SECTION ANSWERS TO EXERCISES ANSWERS TO PROBLEMS INDEX

Abstract: P.C. Gillette, J.B. Lando, and J.L. Koenig, A Survey of Infrared Spectral Data Processing Techniques. P.L. Polavarapu, Fourier Transform Infrared Vibrational Circular Dichroism. K. Krishnan, Advances in Capillary Gas Chromatography*b1Fourier Transform Interferometry. A.G. Nerheim, Applications of Spectral Techniques to Thermal Analysis. P. Painter, M. Starsinic, and M. Coleman, Determination of Functional Groups in Coal by Fourier Transform Interferometry. J.R. Ferraro and A.J. Rein, Applications of Diffuse Reflectance Spectroscopy in the Far-Infrared Region. J.D. Swalen and J.F. Rabolt, Characterization of Orientation and Lateral Order in Thin Films by Fourier Transform Infrared Spectroscopy. W.G. Golden, Fourier Transform Infrared Reflection*b1Absorption Spectroscopy. J.A. Graham, W.M. Grim III, and W.G. Fateley, Fourier Transform Infrared Photoacoustic Spectroscopy of Condensed-Phase Samples. Each chapter includes references. Index.

Abstract: 17O-NMR spectroscopy has found limited application as a structural probe due to the experimental problems associated with a quadrupolar nucleus having low natural abundance. A survey of data obtained from systematic studies of structurally related compounds shows, however, that large chemical shift differences are usually obtained for structurally nonequivalent nuclei, and that characteristic chemical shift values are observed for specific chemical environments. The present day availability of 17O enriched materials and Fourier transform NMR instrumentation should allow extensive application of the 17O-NMR technique to structural problems in the immediate future.

Abstract: The recent demonstration of stimulated Raman gain (loss) spectroscopy (SRS) using CW laser sources introduces a powerful tool to coherent Raman spectroscopy. In this paper we undertake an experimental and analytical evaluation of several variations of SRS using CW laser sources including (1) direct stimulated Raman gain (loss) measurements, (2) optically heterodyned polarization interferometry, and (3) two-beam nonlinear interferometry. The results show CW SRS to be a convenient and effective means of obtaining direct Raman spectra in applications where background fluorescence precludes the use of conventional Raman techniques. Sensitivities comparable to or exceeding those obtained by coherent anti-Stokes Raman spectroscopy (CARS) are demonstrated. Ultimate sensitivities exceeding those achieved by spontaneous Raman spectroscopy are expected for high-resolution applications in gaseous media.

Abstract: Non-Rydberg effects in the photoabsorption spectra of atoms are described. They are observed at photon energies which correspond to the creation of a vacancy within the subvalence shells of the atom or to the simultaneous excitation of two electrons. The importance of synchrotron radiation as an experimental tool for the investigation of non-Rydberg effects is stressed, and many examples are given. Many of the non-Rydberg properties can be understood by analogy with elementary one dimensional potential well theory.

Abstract: This text begins with the mathematical and physical apparatus encountered in most first courses in molecular quantum mechanics. The first nine chapters provide an introduction to research monographs of Herzberg and others in the field. Included here are discussions of radiationless transitions, photoelectron spectroscopy, and other topics not usually considered in texts at this level. Chapters on the latest research and methods in the field--molecular beam and optical pumping spectroscopy, masers and lasers, and multiphoton spectroscopy--follow. The analogy of simple magnetic resonance spectroscopy to optical spectroscopy is explained using the Feynman-Vernon-Hellwarth theorem and then applied to saturation, self-induced transparency, and photon echoes.The author writes that the book "is the outgrowth of several iterations of a one-semester graduate course in molecular spectroscopy at the Massachusetts Institute of Technology, with supplementary material added. The emphasis of the course was on introducing students to the concepts and the methods of modern molecular spectroscopy so that the language would be familiar when the course proceeded to discuss quantum electronics, lasers, and related coherent and nonlinear optical phenomena."

Abstract: We have measured the carbon $K$ edge in graphite using inelastic-electron-scattering spectroscopy. The extended x-ray absorption fine structure is in good agreement with theory for the first-neighbor atoms at a distance of 1.42 \AA{}. The momentum dependence of the edge structure is in qualitative agreement with a simple band-structure picture. A comparison of the signal counting rates for electron-energy-loss and photoabsorption experiments shows that the energy-loss method is competitive with synchrotron radiation sources up to about 1000 eV.

Abstract: Both O(3P) and O(1D) atom fragments are observed in the photofragment spectroscopy of O3 in the Hartley band absorption region 270–300 nm. The quantum yield for O(3P) is 0.1 at 274 nm. The dissociation partner for O(3P) is O2(X3Σ−g) and that for O(1D) is O2(a 1Δg). The O2(X 3Σ−g) fragment is populated in a range of vibrational levels, v?0−10. For the O2(a 1Δg) fragment, all energetically accessible vibrational levels are populated at each energy of bombardment. In the Chappuis bands at 600 nm the O2(X 3Σ−g) photofragment is produced principally with v=0, 1. Photofragment angular distributions are measured in the uv for both O atom dissociation products at each wavelength of bombardment. A theoretical angular distribution for O(1D) is derived and the resultant prediction is in good agreement with the experimental results.

Abstract: Auger-electron spectroscopy is shown to measured something quite different from photoemission: the distribution of atomic (as opposed to overlap) charge populations across the valence bands. While matrix-elements effects must be considered in s-p band materials, their inclusion in calculations still lead to poor agreement with experiment. Good agreement may obtained, however, if one divides the electronic charge into atomic and overlap (bonding) LCAO components and notes that the latter does not contribute to the Auger current.

Abstract: Laser-excited atomic fluorescence flame spectrometry with a pulsed nitrogen laser pumped tunable dye laser has been investigated with respect to analytical figures of merit, especially in terms of improvement of detection limits. The detection limits for 19 elements in an air-acetylene flame and for 5 elements in a nitrous oxide-acetylene flame are evaluated in the cases of both resonance and nonresonance atomic fluorescence lines. The detection limits obtained have been improved about 10 to 200 times. Detection limits for many elements excited by the frequency doubled dye laser output are reported for the first time. Now, most elements examined can be detected at the ng ml/sup -1/ (ppB) level or less with analytical curve linearities of over five orders of magnitude. Improvement of the detection limits was achieved mainly by expanding the diameter of the laser beam to illuminate a larger analyte volume in the flame and by using a low dispersive spectrometric system. The optical arrangement employed reduced the scatter signal and improved the signal-to-noise ratio (SNR). Although a low dispersive spectrometric system (spectral bandwidth of ..delta..lambda/sub M/) was employed, the spectral resolution of the system was determined by the spectral bandwidth of the laser, ..delta..lambda/sub L/(..delta..lambda/sub L/ muchmore » less than ..delta..lambda/sub M/). Conditions for optimizing analytical results are discussed. The results indicate that laser-excited atomic fluorescence spectrometry is potentially superior to atomic absorption spectrometry, atomic emission flame spectrometry, atomic emission induction coupled plasma spectrometry, and conventional source atomic fluorescence spectrometry, in terms of analytical figures of merit.« less

Abstract: The fluorescence spectra, branching ratios, and decay of the /sup 4/F/sub 3/2/ state of Nd/sup 3 +/ in glass were measured under excitation by tunable pulsed laser radiation. The following glass types were studied: silicate, phosphate, borate, fluoroberyllate, and fluorophosphate. Measurements were made at liquid-helium temperatures by exciting into the /sup 2/P/sub 1/2/ state, and line-narrowed fluorescence spectra were obtained as a function of excitation wavelength. Large variations in Stark splitting of the /sup 4/I/sub 9/2/ and /sup 4/I/sub 11/2/ states have been observed and attributed to site-to-site differences in the local crystal field. The probabilities for radiative decay and for nonradiative decay by multiphonon emission also exhibit variations with excitation wavelength. Although similarities exist, each different glass type shows its own distinctive patterns of variation in crystal-field splitting and relative quantum efficiency. In the fluorophosphate glass, which contains large numbers of both fluorine and oxygen anions, comparison of the laser-excited fluorescence spectra and lifetime of Nd/sup 3 +/ with the corresponding results from pure oxide and fluoride glasses demonstrates the presence of Nd/sup 3 +/ sites having both fluorine and oxygen nearest-neighbor coordination.

Abstract: The measured intensities of certain gamma rays of specific energies escaping from a planetary surface can be used to determine the abundances of a number of elements The fluxes of the more intense gamma-ray lines emitted from 32 elements were calculated using current nuclear data and existing models for the source processes The source strengths for neutron-capture reactions were modified from those previously used The fluxes emitted form a surface of average lunar composition are reported for 292 gamma-ray lines These theoretical fluxes were used elsewhere to convert the data from the Apollo gamma-ray spectrometers to elemental abundances and can be used with measurements from future missions to map the concentrations of a number of elements over a planet's surface Detection sensitivities for these elements are examined and applications of gamma-ray spectroscopy for future orbiters to Mars and other solar-system objects are discussed

Abstract: Applications and limitations of optical spectroscopy for process control, as well as for more fundamental investigations, of glow discharge sputter deposition and emission spectroscopies allows the determination of concentrations and spatial distributions of sputtered and background gas species in ground, metastable, ionized, and excited states Optical probing is a sensitive detection technique with good spatial resolution It has the advantage of providing in situ real time information without disturbing the discharge Examples of processes which may be monitored optically include: sputter etching and film deposition rates, net elemental sticking probabilities during bias sputter deposition, plasma ’’ashing’’ of photoresists, and reactive ion etching Optical spectroscopy has also been used as a diagnostic technique for investigating preferential sputtering of alloys, reactive gas–surface interactions, and for providing quantitative chemical analysis and depth profiling information

Abstract: The spectrum produced in the afterglow of an O2-He discharge was studied for the range 4000-8000 A. Lawrence et al. (1977) established that under the appropriate conditions the O2(c 1Sigma u - to X 3Sigma g -) system could be observed in this region. The present study has duplicated these results and has discovered three O2 band systems not previously seen in gas phase laboratory spectra. These systems are C 3Delta u-a 1Delta g, C 3Delta u-X 3Sigma g -, and c 1Sigma u - to a 1Delta g.

Abstract: Interaction of atoms with two intense coherent time-delayed short pulsed standing waves produces quantum interference effects in the atomic fluorescence This type of quantum interference effect applied to Doppler-free two-photon spectroscopy (an extension of the Ramsey method of separated rf or microwave fields in atomic beam experiments) offers a number of important improvements in the presently available techniques of ultra-high-resolution spectroscopy of atoms, molecules, and crystals

Abstract: With the availability of Fourier transform spectrometers, 23Na-NMR spectroscopy has become an important tool. It affords direct insight into solvation and ion pairing phenomena, both in organic and in bio-inorganic systems. Monitoring the chemical shifts and linewidths of 23Na signals gives access to binding constants, reorientational correlation times and the microdynamics of the sodium coordination shell. The binding of other cations can also be studied by 23Na-NMR spectroscopy, in competition experiments.