bluuebunny/crossref_metadata_2025 huggingface dataset:
Fast and Ultrafast Time‐Resolved Mid‐Infrared Spectrometry Using Lasers
Authors: Grills D.C. , George M.W.
Published: September 2006

The sections in this article are

Introduction

Fast

TRIR

Spectroscopy

Fast
TRIR
Spectroscopy Using
IR
Lasers

CW

CO
Lasers

CW

CO
2
Lasers

Tunable

IR

Diode Lasers

Color Center Lasers

Difference Frequency Generation

Ultrafast
TRIR
Studies

Two‐Dimensional

IR

Spectroscopy

Conclusions
Array Detectors forRaman Spectroscopy
Authors: Pommier Carolyn J.S. , Walton Linda K. , Ridder Trent D. , Denton M. Bonner
Published: September 2006

The sections in this article are

Introduction

Noise

Sample Shot Noise

Background Shot Noise

Detector Noise

Dark Current

Read Noise

Pixel‐to‐Pixel Response

Single‐Channel Detectors

Multichannel Detectors

Photographic Emulsions

Resistive Anode Photomultiplier Tubes

Array Detectors

Photodiode Arrays

Quantum Efficiency

Dark Current and Read Noise

Intensified Photodiode Arrays

Charge Coupled Devices

Array Formats

Quantum Efficiency

Open Electrode Structure

Photon Penetration Depth

Window Material

Dynamic Range and Resolution

Noise Considerations

Dark Current

Read Noise

Cosmic Ray Events (CREs)

Etalon Interference Patterns

Specialized Readout Modes

Charge Binning

Subarray Readout

Time‐Delayed Integration

Spectral Framing

IntensifiedCCDsfor Time‐ResolvedRaman Spectroscopy

Charge‐Injection Devices

Nonsilicon Devices

Germanium Detectors

Indium Gallium Arsenide Detectors

Platinum Silicide Detectors

Other Nonsilicon Array Detectors

Microchannel Plates (MCPs)

Applications

Chemical Imaging

Simultaneous Spectra Collection

Conclusion
Hyper‐Raman Spectroscopy
Authors: Ziegler L.D.
Published: September 2006

The essential phenomenological characteristics of the nonlinear spontaneous light scattering effect known as hyper‐Raman scattering (HRS) is described in this review. The salient features of the theoretical description of HRS are given within a susceptibility treatment of the induced electrical polarization. Symmetry selection rules and the relation of HRS to Raman scattering are highlighted in this theory section. Experimental considerations for the observation of this higher order Raman effect are considered. Recent applications of this technique to problems of chemical and physical interest are selected to illustrate the utility of this phenomenon. These include HRS studies of crystals, glasses, semiconductors, and liquids. The phenomenon of surface‐enhanced HRS and electronically resonance‐enhanced HRS are also described and illustrated.
Two‐Dimensional Vibrational Spectroscopy by Doubly Vibrationally Enhanced Four‐Wave Mixing
Authors: Wright John C. , Zhao Wei , Murdoch Keith , Besemann Daniel , Condon Nicholas , Meyer Kent
Published: September 2006

The sections in this article are

Introduction

Theory

History

Site Selective Spectroscopy

Multiresonant Electronic Nonlinear Mixing Spectroscopy

Multiresonant Six‐Wave Mixing Spectroscopy and 2
D
R
aman Spectroscopy

Photon Echo and Stimulated Photon Echo Methods

2
D
Correlation Spectroscopies and Femtosecond Pump–Probe Experiments

Experimental

2
D

DOVE

Spectroscopy

Mode Selection in

DOVE

Component and Isotopic Selection in

DOVE

Time Resolved Structure Determinations

Solvent Background Suppression

Line Narrowing

Conclusions

Acknowledgments
Photometric Standards for Raman Spectroscopy
Authors: McCreery Richard L.
Published: September 2006

Correction of Raman spectra for instrument response to produce a spectrum with reliable relative peak intensities is not commonly performed, in part because of experimental difficulty and lack of suitable standards. Procedures are described on the basis of white light sources and on luminescent samples with known output intensity profiles. In the latter case, the procedure is fast and automatic, with an intensity standard merely taking the place of an ordinary sample. In addition to simplicity, the method is more accurate than a white light source because the illumination geometry of the intensity standard is identical to that of the sample. Standards are currently available from National Institute of Standards and Technology (NIST) for several wavelengths, including 785, 532, and 514.5 nm. Spectra of several compounds are provided for determining the accuracy of intensity calibrations, and procedures for deducing the Raman cross section for target materials are described.
Vibrational Spectroscopy at High External Pressures
Authors: Ferraro John R.
Published: September 2006

The sections in this article are

Introduction

Experimental

Instrumentation

Raman Spectroscopy

IR

Spectroscopy

Sample Loading

Pressure Calibration

Discussion and Results

Vibrational Studies of Coordination Complexes

Solid‐State Structural Conversions with Pressure

Spin‐State Changes with Pressure

Oxidation Changes with Pressure

Megabar Pressures

Simulation of Temperature and Pressure Conditions in the Earth's Mantle and Earth's Core

Metalization

Conclusions

Acknowledgments
Matrix Isolation Infrared Spectroscopy
Authors: Willson Stephen P. , Andrews Lester
Published: September 2006

The experimental methods for performing cryogenic matrix‐isolation infrared spectroscopic measurements on reactive species are described. A number of different techniques for preparing reactive species for matrix trapping are presented. Some representative infrared (IR) spectra and 30 references are given.
Long Path Gas Cells
Authors: Hanst Philip L.
Published: September 2006

The sections in this article are

A Long Path is Needed for Gas Measurement

Study of the Atmosphere

Long Path Cells for Laboratory Measurement of Gases (White's Cell)

Some Applications

Variations onWhite's Cell

Two Rows of Images

Four Rows of Images

Six Rows of Images

Wilks–Foxboro Cell

Many‐Mirror Systems

Use of One Focusing Mirror

The Flexible Mirror

Long Path Cells for Use with Lasers (Herriott's Cell)

Cell Construction Techniques and Materials

Cell Alignment

Heating ofWhite Cells

Cell Maintenance and Restoration
External Reflection Spectroscopy
Authors: Claybourn Mike
Published: September 2006

The sections in this article are

Introduction

Making Reflectance Measurements

Reflectance and Anomalous Dispersion

The Origin and Description of the
F
resnel Formulae

Reflection of Light from a Material with Absorption Bands

Reflectance at the
B
rewster Angle

The Complex Angle of Refraction

Reflectance from a Multilayered System

Measurements at Normal Incidence

Polarized Reflectance Measurements for θ > 20°
Polarization‐Modulation Approaches to Reflection–Absorption Spectroscopy
Authors: Frey Brian L. , Corn Robert M. , Weibel Stephen C.
Published: September 2006

The sections in this article are

Introduction to Polarization‐Modulation Reflection–Absorption Spectroscopy

Experimental Considerations for the

PM

‐

IRRAS

Measurement

Experimental Setup

The

PEM

The

PM

‐

IRRAS

Measurement

PM

‐

IRRAS

Spectral Normalization

Examples and Applications of

PM

‐

IRRAS

Measurement

Metal Surfaces – Ex Situ

Self‐Assembled Monolayers in the
CH
Stretching Region

SAMs

in the Fingerprint Region

Metal Surfaces – Liquid Phase In Situ

Structural Studies of

SAMs

Electrochemical Studies

Metal Surfaces – Gas Phase In Situ

Corrosion Studies on Copper

Carbon Monoxide on
Co
(0001)

Organic Vapors on Silicon Dioxide Nanoparticle Thin Films on Gold

Air/Water Interface
Macro and Micro Internal Reflection Accessories
Authors: Fitzpatrick James , Reffner John A.
Published: September 2006

The sections in this article are

Introduction

Internal Reflection

Historical Development of Internal Reflection Apparatus for Recording
ATR
Spectra

The Impact of the
FT
‐
IR
Revolution on Internal Reflection Accessories

Chemical Analysis
vs
Determination of Optical Properties

Advances in Materials for

IRE

s

Internal Reflection Accessories for Laboratory Spectrometers

Macro‐Sized Sample Analysis

Prism

Trapezoidal

Cylindrical

Hemispherical

Micro‐Sized Sample Analysis

ATR

Objectives for Microscopes

Internal Reflection in Chemical Process Analyses

New Developments in Internal Reflection Attachments and Systems
Internal Transmission Spectroscopy
Authors: Chabal Yves J.
Published: September 2006

The sections in this article are

Introduction

Theory

The Linear Approximation

Buried Interface: Three‐Layer Model

Interface in Proximity of a Surface: Four‐Layer Model

Examples

Experimental Verification of Enhancement

Silicon Wafer Bonding

Hydrogen‐Induced Exfoliation

Outlook

Acknowledgments
Accessories and Sample Handling for Mid‐Infrared Diffuse Reflection Spectroscopy
Authors: Milosevic Milan , Berets S.L.
Published: September 2006

The sections in this article are

Introduction

Theory

Sample Handling

Sample Preparation

Sample Thickness

Penetration Depth in Diffuse Reflection

Spectroscopic Sensitivity in Diffuse Reflection Spectroscopy

Optical Design of Diffuse Reflection Accessories

Diffuse Reflection Accessories for Spectrometers

Specular Reflection and Anomalies in Diffuse Reflection Spectroscopy

Commercially Available Diffuse Reflection Accessories

Overview

PrayingMantis™

Selector™

Collector™

BarrelEllipsoid™

Low‐Cost Diffuse Reflection Accessories

Conclusion
SERS‐BasedRaman Probes
Authors: Vo‐Dinh Tuan , Stokes David L.
Published: September 2006

The sections in this article are

Introduction

DifferentSERS‐Based Probes

Metal Electrodes

Metal Colloids

SolidSERSProbes Based on Metallic Nanostructures

Metal Nanoparticle Island Films

Silver‐Coated Nanosphere Probes

Metal‐Coated NanoparticleSERSProbes

SERSProbes Based on Metal‐Coated Quartz Posts

SERSProbes Based on Chemically and Abrasively Roughened Solid Surfaces

SERSProbes Based on Inherently Rough Materials

SERS‐Based Probes Based on Metal Nanoparticle‐Embedded Media

SERSProbe Coatings

General Organic, Metallic and Dielectric Coatings

SAMs

Monolayers of Bioreceptors

Advanced Sensing Technologies Based onSERSProbes

Remote Fiber OpticSERSMonitors and Nanosensors

Dual‐Fiber Systems

Integrated Single‐Fiber System and Nanosensors

Surface‐EnhancedRaman Scattering‐Scanning Near‐Field Optical Microscopy

Conclusion

Acknowledgments
Mid‐Infrared Transmission Microspectroscopy
Authors: Sommer André J.
Published: September 2006

The sections in this article are

Introduction

History

Instrumentation

Objectives

Apertures or Field Stops

System Layout and Magnification

Detectors

Automation

Performance Evaluation

Applications and Sampling Modes

Transmission Microspectroscopy

Reflection Measurements

Quantitative Measurements

New and Future Directions
R
aman Microscopy
Authors: Dhamelincourt Paul
Published: September 2006

After a brief recall of the history of Raman spectroscopy, the article presents a summary of the most recent developments in micro‐Raman instrumentation – point analysis and imaging techniques – including the use of confocal optics and line illumination that are now available in most of the commercial instruments.

Some examples of Raman mapping are presented, illustrating the powerfulness of the Raman technique.
Fiber‐Optic Probes for Mid‐Infrared Spectrometry
Authors: Melling Peter J. , Thomson Mary
Published: September 2006

The article discusses the optical design of mid‐IR (infrared) fiber‐optic probes for chemical analysis, including the advantages of using fiber bundles and the importance of fiber numerical aperture. The design of, and available materials for, 2‐ and 3‐bounce attenuated total reflection (ATR) crystals to be used with the probes are discussed and their penetration depth and sensitivity are compared. The stability, reproducibility, and transfer of calibrations and the design of probe heads for extreme conditions of temperature, pressure, and chemical corrosiveness are described. The following applications are discussed: surface analysis and cleaning validation using a grazing‐angle head, polymer curing, air‐free and low‐temperature studies, human skin, and fermentation monitoring.
Sensor Systems Based on Mid‐Infrared Transparent Fibers
Authors: Mizaikoff Boris , Lendl Bernhard
Published: September 2006

The sections in this article are

Introduction

Some Basic Remarks on Optical Sensor Systems

Brief History

Basic Sensing Principle

Sensing Schemes

MIR

Sensors Based on Direct Analyte Interaction

Chalcogenide Fiber Based Direct Sensors

Fluoride Fiber Based Direct Sensors

Sapphire Fiber Based Direct Sensors

Tellurium Halide Fiber Based Direct Sensors

Silver Halide Fiber Based Direct Sensors

Hollow Waveguide Based Direct Sensors

Chemical

MIR

Sensors and Complex Matrices

Biological/Biochemical Applications

Medical Applications

Environmental/Process Applications

Mid‐Infrared Sensors Combined with Flow Injection Analysis

Determination of Enzyme Activities

Determination of Phosphate in Dietary Soft Drinks

Automated Solvent Exchange During the Determination of Caffeine in Soft Drinks

Future Perspectives

Conclusion
Depth Profiling by Photoacoustic Spectroscopy
Authors: Urban Marek W.
Published: September 2006

The sections in this article are

Introduction: Origin and Principles of Photoacoustic Spectroscopy

PA

Experimental Methods

CS
FT
‐
IR
PA
Methods

S
2
FT
‐

IR

PAS
Methods

S
2
PAS
Phase Analysis

Applications to Surface Depth Profiling
Directly‐Linked Gas Chromatography–Infrared–Mass Spectrometry (GC/IR/MS)
Authors: Wilkins Charles L.
Published: September 2006

Directly linked gas chromatography‐infrared‐mass spectrometry (GC/IR/MS) is well established as a technique that fills a unique niche in the field of complex mixture analysis and structure elucidation. Although the method is not well suited for trace analysis, it has proved especially useful for analytical applications that are not sample limited. Commercial analysis systems based on this approach have gained acceptance and it is expected that continuing advances in the fields of chromatography and spectral detection will lead to improved GC/IR/MS systems in the future. This article reviews the history of GC/IR/MS development and briefly surveys the various approaches including lightpipe and matrix isolation methods. The use of complementary information is stressed and multidimensional GC/IR/MS discussed. Examples of applications include flavor and fragrance analysis, isomer identification, and pyrolysis product identification.
SFC
/
FT
‐
IR
(Flow‐Cell and Direct Deposition)
Authors: Bartle Keith D.
Published: September 2006

Supercritical fluids (SF) have properties that are an intermediate between those of gases and liquids and are, therefore, useful mobile phases for chromatography, producing high‐resolution separations of less‐volatile compounds. Fourier transform infrared (FT‐IR) spectrometry is a powerful and specific detection technique for supercritical fluid chromatography (SFC), providing a nondestructive universal detection method from total infrared (IR) absorption, and analyte identification from libraries of spectra. Two procedures are employed in SFC/FT‐IR: flow cells (volume 800 nL for capillary column work) with ZnSe windows allow SFC with CO
2
mobile phase, which absorbs weakly in the mid‐IR, although SF xenon is also effective and IR transparent, if expensive; a solvent‐elimination interface permits the use of CO
2
with an organic modifier because each chromatographic peak is deposited from a restrictor onto a movable KBr or ZnSe plate from which spectra may be recorded without solvent interference by means of an FT‐IR microscope. Satisfactory spectra have been recorded from low‐nanogram amounts by both methods. Among numerous application areas, polymer chemistry has proved to be the most fruitful.
R
aman‐Detected Capillary Electrophoresis
Authors: Morris Michael D.
Published: September 2006

The sections in this article are

Introduction

Safety Considerations

Capillary Zone Electrophoresis/
R
aman Spectroscopy

Capillary Zone Electrophoresis/Surface‐Enhanced
R
aman Spectroscopy

R
aman/Isotachophoresis

Microchip
R
aman/Isotachophoresis

Conclusions
Thin Layer Chromatography and Vibrational Spectroscopy
Authors: Chalmers John M.
Published: September 2006

Thin layer chromatography (TLC) is a widely used separation technique for mixtures of non‐volatile organic molecules. This article discusses the synergy between the selectivity of TLC and the specificity of vibrational spectroscopy techniques. It focuses, in particular, on approaches for combining these two disciplines to enhance analytical studies, their limitations and example applications.
In situ
methods for identifying TLC separated components (spots) are problematic using most commercial TLC plates, because most common TLC stationary phases and binders absorb strongly infrared radiation. Also many are highly fluorescent making some Raman
in situ
characterisations difficult. For mid‐infrared identifications, both spot removal methods and chromatogram transfer techniques are described, in which the separated eluates (spots, analytes) are removed or transferred onto more suitable substrates for examination by conventional mid‐infrared methods such as alkali‐halide disks or diffuse reflection. Use of alternative stationary phases, such as zirconium oxide, for enabling
in situ
mid‐infrared spectroscopic measurements is also considered. The feasibility and potential of using near‐infrared spectroscopy as a detection technique for TLC spots is also discussed. Raman studies have focused almost exclusively on
in situ
measurements, although, in general, there is a mismatch between a typical TLC spot size and the diameter of the Raman excitation laser beam at the sample point focus.
In situ
FT‐Raman spectroscopy examine a larger sample area and have the added advantages of ameliorating fluorescence and laser‐induced sample damage. Enhanced sensitivity with Raman can be achieved using resonance Raman, and the surface enhanced techniques of SERS and SERRS.
Transient Infrared Spectroscopy
Authors: Jones Roger W. , McClelland John F. , Bajic Stanley J.
Published: September 2006

The sections in this article are

Introduction

Theoretical Considerations

Physical Considerations

Capabilities

Applications

Laboratory Examples

On‐Line Examples

Acknowledgments
Photoacoustic Spectroscopy
Authors: McClelland John F. , Jones Roger W. , Bajic Stanley J.
Published: September 2006

The sections in this article are

Introduction

Photoacoustic Signal Generation, Processing, and Interpretation

Instrumentation

Sample Considerations

Applications

Application 1

Application 2

Application 3

Application 4

Application 5

Application 6

Conclusion

Acknowledgments
Lidar and Laser Remote Sensing
Authors: Killinger Dennis K.
Published: September 2006

Lidar or laser remote sensing involves the use of a laser beam as an optical probe of the surrounding environment and as a spectroscopic sensor of gases and constituents from afar. This chapter covers the basic techniques used for remote sensing of distant targets and surrounding atmospheric gases, but with an emphasis on the aspects of lidar that uses unique vibrational and rotational optical spectroscopy either in absorption or in Raman scattering. The basic physics of laser remote sensing is covered including that associated with the development of tunable laser sources, line width and wavelength parameters, atmospheric transmission through different atmospheric conditions of fog and gas cloud concentrations, and the detection of the lidar backscattered radiation. Aspects of the lidar equation are presented to help predict the signal‐to‐noise ratio (S/N) of the remote sensing signal, the influence and trade‐offs of using different targets (hard targets or atmospheric aerosols) and the use of different spectroscopic interactions including Raman, fluorescence, and nonshifted backscattered lidar radiation. Examples of current research using differential‐absorption lidar (DIAL) and Raman spectroscopic measurements are presented with specific examples of the remote sensing of NH
3
clouds and CO
2
in the atmosphere. Finally, the important role that the development of new tunable lasers plays in lidar sensing is emphasized.
Spectra–Structure Correlations in
R
aman Spectroscopy
Authors: Edwards H.G.M.
Published: September 2006

The article sets out to examine the effects of instrumental parameters on the observation of Raman spectral bands and of the importance of recognition of the presence of chemical functionality in specimens. Specific examples are considered using CO, CC, SS, and aromatic ring vibrations, especially where the adjacent positions or conjugation of these moieties creates wavenumber shifts in the observed spectra; predictions for the latter are considered alongside electronic, geometric, and mechanical aspects of the molecular structures of key compounds. Substituent‐sensitive Raman bands for aromatic ring vibrations are also discussed. Finally, some applications of the adoption of Raman spectra–structure correlations in real‐world examples taken from diverse areas are given, including the biodeterioration of rock substrata by invasive organisms, Shergotty–Nakhla–Chassigny (SNC) Martian meteorites, and the identification of genuine works of art from fakes. Tables of Raman wavenumbers of some important bonds in inorganic molecules and molecular ions and organic compounds are provided.
Infrared and
R
aman Spectra of Inorganic and Coordination Compounds
Authors: Nakamoto Kazuo
Published: September 2006

Inorganic molecules (ions) and ligands are classified into diatomic, triatomic, four‐atomic, five‐atomic, six‐atomic, and seven‐atomic types, and their normal modes of vibration are illustrated and the corresponding vibrational frequencies are listed for each type. Molecules of other types are grouped into compounds of boron, carbon, silicon, nitrogen, phosphorus, and sulfur, and the structures and infrared (IR)/Raman spectra of select examples are shown for each group. Group frequency charts including band assignments are shown for phosphorus and sulfur compounds. Other group frequency charts include hydrogen stretching frequencies, halogen stretching frequencies, oxygen stretching and bending frequencies, inorganic ions, and metal complexes containing simple coordinating ligands.
Automated Spectral Searching in Infrared,
R
aman and Near‐Infrared Spectroscopy
Authors: Lowry Stephen R.
Published: September 2006

The sections in this article are

Introduction

Spectral Search Algorithms

Peak Location Search

Spectral Searching with Peak Tables

Using the Full Spectrum for Searching

Preprocessing and Spectral Standardization

Resolution and Data Compression

Baseline Correction for Spectral Searching

Intensity Normalization for Spectral Libraries

Creation of Spectral Search Libraries

Sampling Technique

Spectral Range and Format

Intensity and Linearity

Physical Property Information

Mid‐Infrared Spectral Searching

Overview

An Example of

MIR

Spectral Searching

Near Infrared Spectral Searching

Overview

Special Considerations for

NIR

Searching

NIR

Search Example

Spectral Searching with
R
aman Spectra

Overview

Special Considerations for
R
aman Searching

An Example of
R
aman Spectral Searching

Conclusions
Utility of Isotopic Data
Authors: Durig James R.
Published: September 2006

The sections in this article are

General Information

Vibrational Assignments

Vibrations with Near‐Zero Intensities

Torsional Modes

Metal–Ligand Modes

Distinguishing Optical Translations from Librational Modes

Determination of Molecular Symmetries

MHDistances (M = C,Si,Ge)

Carbon–Hydrogen Distances

Silicon–Hydrogen Distances

Other Atom–Hydrogen Distances

Theory
Calculation of Vibrational Frequencies by
H
artree–
F
ock‐Based and Density Functional Theory
Authors: Matsuura Hiroatsu , Yoshida Hiroshi
Published: September 2006

The sections in this article are

Introduction

Historical Overview

Theoretical Overview

HF

Force Constants

Density Functional Force Constants

Basis Sets

Calculation of Vibrational Frequencies by

HF

‐Based Theory

SQM

Method

SQM

Force Fields for π Electron Systems

Calculation of Vibrational Frequencies by

DFT

Performance of

DFT

Calculation

Evaluation of Functionals and Basis Sets

A New Approach to Vibrational Analysis by

DFT

WLS

Method
Calculation of Vibrational Frequencies by Molecular Mechanics
Authors: Hotokka Matti
Published: September 2006

The molecular mechanics (MM) method is a purely classical ball‐and‐spring model as opposed to the quantum chemical computational methods. The MM energy is formed as a sum of terms based on parameters such as the stiffness and equilibrium value of the chemical bonds, bond angles, torsions etc. Therefore, the success of the MM method depends on the flexibility of the parameterization or the force field. The basic principles of the MM method and a few examples of the available force fields are presented. The MM method is shown to offer a cost‐effective way of calculating the vibrational frequencies quite accurately. The band intensities may also be estimated.
Smoothing and Derivatives in Spectroscopy
Authors: DeNoyer L.K. , Dodd Jack G.
Published: September 2006

A review of classic methods for smoothing and derivatives is given in parallel with a presentation of new maximum likelihood, maximum entropy, and Bayesian smoothing and derivative methods. The fundamental equations for maximum likelihood and maximum entropy smoothing and equations for Bayesian derivatives are provided. Classic smoothing methods are compared to linearized maximum entropy smoothing by examining the equivalent Fourier filters. Tables show details of the peak widening effects of classic smoothing against the resolution preservation of maximum entropy smoothing. Likewise, figures illustrate the contrast between the loss of resolution and noisy character of Savitzky–Golay derivatives versus the resolution‐preserving and superior noise performance of Bayesian derivatives. The authors provide some philosophy on when to smooth, when to fold, and what to ask of a smoothing method.
Curve‐Fitting: Modeling Spectra
Authors: Dodd Jack G. , DeNoyer L.K.
Published: September 2006

Practical advice on fitting peak models to data is given—how to choose the peak shapes, which algorithms to use, the sensitivity of different parameters to initial conditions, avoiding overfitting. Perhaps the most important advice of all discusses the frequently applied tactic of smoothing prior to fitting.
B
eer's Law
Authors: Griffiths Peter R.
Published: September 2006

Beer's law is the fundamental law of quantitative absorption spectroscopy because it relates the absorbance to the product of the concentration of each analyte and the pathlength of the cell. In this article, the theoretical requirements for Beer's law to be obeyed are given; these include the need for a collimated beam of monochromatic radiation and the need for a dilute homogeneous solution of the analyte. In practice, these requirements can be relaxed but in order for Beer's law to be obeyed, interaction between the analyte molecules that can cause the absorptivity to change as a function of concentration must be constant. The optimum condition for quantitative spectroscopy is found when the transmittance is equal to 1/
e
. Baseline correction is sometimes needed to obtain the optimum result, but this may at times be a subjective operation. Instrumental effects on Beer's law linearity are discussed in some detail. For measurements of concentrated solutions made with a monochromator, the effect of stray radiation may be significant. The effect of instrumental resolution on Beer's law linearity is discussed in terms of the resolution parameter, which is the ratio of the width of the instrument line shape function to the full width of the band. Measuring the spectrum at low resolution only leads to nonlinear Beer's law behavior when the true peak absorbance is greater than about 0.5. Deviations from Beer's law for measurements made with a Fourier transform spectrometer are strongly dependent on the apodization function that is used. The Norton‐Beer medium apodization is recommended for achieving Beer's law linearity over very wide concentration ranges.
Classical Methods of Quantitative Analysis
Authors: Coates John
Published: September 2006

The sections in this article are

Introduction

Fundamental Relationships

The Recorded Spectrum and the Nature of the Measurement

Data Extraction and Preprocessing

Single Component

Two or More Components (Multicomponent)

Instrument Operation and Sample Handling

Instrument Issues

Sample Issues

Gases

Liquids, Semi‐Solids and Slurries

Solids

Calibration Procedures

Sources of Error

The Concept of the Method

Worked Examples
Inverse Least Squares and Classical Least Squares Methods for Quantitative Vibrational Spectroscopy
Authors: Franke James E.
Published: September 2006

The sections in this article are

Introduction

Theory of Inverse Least Squares and Classical Least Squares Methods

Inverse Least Squares Calibration

Inverse Least Squares Prediction

Classical Least Squares Calibration

Classical Least Squares Prediction

Data Preprocessing

Extensions to Basic Inverse Least Squares and Classical Least Squares Methods

Discussion of Inverse Least Squares and Classical Least Squares Methods

Statistical Properties

Advantages and Disadvantages

Performance Comparisons

Application of Multivariate Methods to Spectroscopic Data

Conclusions
Quantitative Spectroscopic Calibration
Authors: Mark Howard
Published: September 2006

After considering the meaning of the term ”calibration” in the context of spectroscopic analysis and the need for the application of ”modern” spectroscopic methods, this chapter provides an overview of the process of applying modern calibration concepts to the task of performing chemical analysis through spectroscopic measurements. The need for good chemical practice (representative sampling, proper sample handling, etc.) combined with the considerations for proper data handling and treatment (number of samples, reference value measurement, preliminary data transformations, etc.) is described and discussed. The bulk of the chapter then addresses the description and behavior of the various mathematical and computer algorithms that are used to relate the spectral data to the composition and properties of the sample.
Measurements of the Chemical Characteristics of Polymers and Rubbers by Vibrational Spectroscopy
Authors: Boerio F. James
Published: September 2006

The sections in this article are

Introduction

Branching and End Groups

Degradation

Stereoregularity

Chain Conformation

Defects in Polymer Conformation

Isomerism in Rubber Compounds

Hydrogen Bonding

Conjugated Double Bonds
Vibrational Spectroscopy of Conducting Polymers
Authors: Furukawa Yukio
Published: September 2006

The sections in this article are

Introduction

Infrared and
R
aman Spectra of Pristine Polymers

R
aman Spectra of Doped Polymers

Doped Polyacetylene

Doped Polythiophene

Doped Poly(

p

‐Phenylene)

Doped Poly(

p

‐Phenylenevinylene)

Doping‐ and Photo‐Induced Infrared Absorption

Infrared Spectra of Injected Carriers

Concluding Remarks
Infrared Spectroscopy in the Study of the Weathering and Degradation of Polymers
Authors: Gardette Jean‐Luc
Published: September 2006

The sections in this article are

Introduction

Identification of Oxidation Products

Infrared Spectra of Oxidized Samples

Chemical Derivatizations

Derivatization Using Sulfur Tetrafluoride

Derivatization Using Ammonia

Derivatization Using Nitric Oxide

Derivatization Using Sulfur Dioxide

Other Methods

Oxidation Mechanisms: Polypropylene Photooxidation

Characterization of Heterogeneous Oxidation

Surface Parallel Analysis

Cross‐Sectional Analysis by Micro‐

IR

Spectroscopy

Photoacoustic

IR

Spectroscopy

Attenuated Total Reflection
Dynamic Infrared Linear Dichroism Spectroscopy
Authors: Marcott Curtis , Noda Isao
Published: September 2006

The sections in this article are

Introduction

IR
Linear Dichroism and Molecular Orientations

Dichroic Parameters

Classical Theory of Linear Dichroism and Molecular Orientation

Limitation of the Classical Theory

Dynamic Mechanical Analysis

DMA
and Viscoelasticity

Mechanical Spectra

Dynamic Infrared Linear Dichroism Spectroscopy

Combination of
IR
Dichroism and
DMA

DIRLD
Spectra

Wavenumber Dependence of β(ν)

Instrumentation

General Considerations for Dynamic
IR
Spectrometers

Dispersive Dynamic
IR
Spectrometer

Mechanical and Thermal Components

Optical Components

Signal Demodulation, Data Acquisition, and Processing

Fourier Transform Dynamic

IR

Spectrometer

Dispersive
vs
Interferometric Instrumentation

Rapid‐Scanning

FT
‐
IR

Spectrometer

Step‐Scanning

FT
‐
IR

Spectrometer

Examples of

DIRLD

Measurements

Measurements with a Dispersive Spectrometer

Measurements with a Fourier Transform Spectrometer

Experimental Procedure

Conclusions
Vibrational Spectroscopy of Carbon and Silicon Materials
Authors: Yoshikawa M. , Nagai N.
Published: September 2006

Vibrational spectra of carbon and silicon materials are introduced in this section.

First of all, origin of Raman and infrared spectra of carbon materials such as graphite, diamond and amorphous carbon films are discussed and then typical examples of characterization by Raman and infrared spectroscopy in these materials are explained in detail. Next, the analytical method to characterize the local residual stress in local oxidation of silicon (LOCOS) and the microstructures in silicon dioxide is demonstrated by using Raman spectroscopy. Finally, we explain the local vibrational modes in silicon crystals and how to analyze surface of silicon crystals and silicon dioxide using infrared spectroscopy. Raman and infrared spectroscopy are useful techniques to characterize carbon and silicon materials.
Raman Spectroscopy of Semiconductors
Authors: Nakashima S. , Harima H.
Published: September 2006

The sections in this article are

Introduction

Structural Characterization of Semiconductors

Fundamentals of PhononRaman Scattering

Determination of Crystallographic Orientation byRaman Polarization Measurement

Raman Image Measurements of Solid‐State GrowthSiFilms

Evaluation ofSiC‐Polytype Structures andGaAsAlAsSuperlattices from theRaman Scattering

Raman Scattering by Phonons in Mixed Crystals

Evaluation of Defects in Semiconductors

Stacking Faults inSiC

Amorphous Semiconductors and Conversion from Amorphous to Crystalline State

Characterization of Electronic Properties in Semiconductors

LO–Phonon–Plasmon Coupled Mode

Conclusion
Vibrational Raman Spectroscopy of High‐temperature Superconductors
Authors: Thomsen C. , Kaczmarczyk G.
Published: September 2006

The sections in this article are

Introduction

R
aman Scattering

Theoretical Approaches to Vibrations in High‐

T

c

Materials

Vibrations in High‐

T

c

Superconductors

YBCO

and Related Compounds

The
Bi
2
Sr
2
Ca

n

 − 1

Cu

n

O

2

n

 + 4

Superconductor Family

Characterization of High‐

T

c

Materials

Foreign Phases

Orientation and Oxygen Content

Epitaxy

Electron–Phonon Interaction

Self‐Energy Effects in High‐

T

c

Superconductors

Acknowledgments
R
aman Spectroelectrochemistry
Authors: Pemberton Jeanne E.
Published: September 2006

The sections in this article are

Introduction

Brief Overview of
R
aman Spectroelectrochemical Approaches

Resonance
R
aman Spectroscopy of Electrochemically Generated Solution Species

SERS

Surface‐Enhanced Resonance
R
aman Scattering

SERS

through Thin Film Transition Metal Electrodes on Enhancing Substrates

Surface Plasmon Polariton Enhanced
R
aman Spectroscopy

R
aman Spectroelectrochemical Emersion

Confocal
R
aman Spectroelectrochemistry

Surface
R
aman Spectroelectrochemistry without Enhancement

Experimental Considerations

R
aman Spectroelectrochemical Cells

Electrode Surfaces and their Preparation

R
aman Systems for Spectroelectrochemistry

Example Applications of
R
aman Spectroelectrochemistry

Characterization of Adsorbed Organics on Electrode Surfaces: 1‐Methylimidazole on
Ag

Characterization of Specifically Adsorbed Ions at Electrode Surfaces

Characterization of Interfacial Solvent Structure at Electrode Surfaces

Characterization of Electrochemical Interfaces Using
R
aman Spectroelectrochemical Emersion
Vibrational Spectroscopy Imaging of Agricultural Products
Authors: Budevska Boiana O.
Published: September 2006

Chemical imaging based on near‐ and mid‐infrared (IR) spectroscopy used for characterization of agricultural products is reviewed. The advantages of Fourier transform infrared (FT‐IR) microscopy compared to traditional methods for characterization of in situ plant tissue are described. Microspectroscopic mapping and imaging measurement approaches are discussed. The impacts of diffraction on the spatial resolution, sample heterogeneity, and other optical effects on the quality of data are discussed. Results from measurements of microtomed plant tissue are reviewed. An example of FT‐IR microspectroscopic images of the endosperm/aleurone/pericarb area of a mature corn kernel measured with a 64 × 64 mercury cadmium telluride focal‐plane array (MCT FPA) detector is presented and discussed in detail. Strategies for converting the FT‐IR hyperspectral data into chemical information are presented.
Process Measurements by Raman Spectroscopy
Authors: Everall Neil , Clegg Ian , King Bert
Published: September 2006

Raman spectroscopy has long been recognized as a powerful analytical tool, capable of characterizing a wide range of materials, but for many years the size and complexity of instrumentation confined it to the research laboratory, making process analysis impractical. However, compact, sensitive and robust Raman instruments are now available that can be readily interfaced to production processes. This article attempts to illustrate the general capabilities of Raman spectroscopy as a process analytical tool. We first consider the instrumental and engineering aspects of making Raman measurements under production conditions, and then discuss some of the areas in which it has been fruitfully employed. The application examples discussed were chosen to cover the main range of sample types that one might encounter in the industry. We also describe some common artifacts and problems, which can arise and confuse the new practitioner.
Passive Remote Sensing by
FT
‐
IR
Spectroscopy
Authors: Combs Roger J. , Kroutil Robert T. , Small Gary W.
Published: September 2006

The sections in this article are

Introduction

Radiance Model

Passive Sensor Performance Evaluation

Remote Sensor Instrumentation

Signal Analysis Strategies

Remote Sensing Measurements

Conclusions
Vibrational Spectroscopy in the Automotive Industry
Authors: Carter Roscoe O. , Weber Willes H.
Published: September 2006

Vibrational spectroscopy forms the basis for many of the analytical tools used in the automotive industry. These tools are divided naturally into those designed for gas‐phase studies and those for condensed‐matter investigations. The gas‐phase infrared measurements include speciation and time‐resolved studies of the chemistry of smog formation and the chemistry of hydrofluorocarbons and related compounds. The section concludes with a novel account of using gas‐phase Raman to test seals in micromachined devices. The condensed‐matter studies include catalyst materials, paints and other thin‐film coatings, plastics, and friction and wear interfaces and are among the topics discussed in this section. Improved functionality and/or durability of materials motivate most of these studies, but the identification for recycling purposes is also an issue. The authors have a combined 50 years of experience applying vibrational spectroscopy to a wide variety of problems. The topics chosen for discussion are focused on those investigations in which the authors or their colleagues have been directly involved. Thus, the review is not meant to be comprehensive.
Vibrational Spectroscopy of Supported Metal Catalysts
Authors: Kennedy Sinéad A. , Hollins Peter
Published: September 2006

The sections in this article are

Introduction and Historical Perspective

Experimental Techniques

Transmission Infrared Spectroscopy

Diffuse Reflection Infrared Fourier Transform Spectroscopy(DRIFTS)

Infrared Microscopy

Infrared Emission Spectroscopy

Raman Spectroscopy

Inelastic Neutron Scattering

Inelastic Electron Tunneling Spectroscopy

Physical Principles

The Metal–Surface Selection Rule

Dipolar Coupling Effects

Applications

Carbon Monoxide Adsorption

Methanol Synthesis

Conclusion
Pathology by Infrared and
R
aman Spectroscopy
Authors: Jackson Michael , Mantsch Henry H.
Published: September 2006

The sections in this article are

Introduction

Historical Perspective

IR

R
aman

Applications of Vibrational Spectroscopy in Pathology

Sample Preparation

Representative Examples

Analysis of Biological Fluids

Analysis of Cells

Analysis of Tissues

Microscopic Techniques

Point Spectroscopy

Mapping/Imaging

Spatial Resolution, Spectral Resolution, Signal‐to‐Noise Ratio and Acquisition Time

Summary and Prospects for the Future
Glucose Measurements by Vibrational Spectroscopy
Authors: Heise H.M.
Published: September 2006

The aldohexose glucose is the most abundant monosaccharide in physiological samples because of its metabolic importance for eucaryotic cells.d‐Glucose exists in two stereoisomer forms, that is, theα‐ andβ‐anomers, which also show differences in their vibrational spectra. The mid‐ and near‐infrared spectra and the Raman spectra are presented in comparison mainly to the hexose of fructose (a furanose). Spectral data are illustrated for the crystalline substance and for glucose in aqueous solutions. The latter spectra are important for analytical applications within the life science area for reagent‐free spectroscopic assays, competing with conventional enzyme‐based amperometric biosensor technologies. For quantitative biofluid analysis, multivariate calibrations are usually employed to achieve the required assay selectivity. Besides biotechnological applications clinical methods are also described, which aim at the analysis of whole blood and derived fluids, and of others such as urine or the aqueous humour of the eye. In addition, activities with regard to noninvasive blood glucose measurements are described.
Vibrational Spectroscopic Studies of Microorganisms
Authors: Maquelin K. , Choo‐Smith L.‐P. , Kirschner C. , Ngo‐Thi N.A. , Naumann D. , Puppels G.J.
Published: September 2006

The sections in this article are

Introduction

FT‐IRandRaman Spectroscopic Studies of Microorganisms

Chemical Structures and Composition of Microbial Cells

Main Biological Building Blocks

Experimental Methodologies ofIRandRaman Spectroscopy

Absorption/Transmission (A/T)IRSpectroscopy

Absorption/Reflection (A/R)IRSpectroscopy

Attenuated Total Reflection(ATR)IRSpectroscopy

Diffuse Reflection(DR)IRSpectroscopy

IRMicrospectroscopy

Ultraviolet ResonanceRaman Spectroscopy

Fourier TransformRaman Spectroscopy

NIRMultichannelRaman Spectroscopy

Sampling of Microbial Cells

Reproducibility of Measurements on Microorganisms

Data Analysis Used for Characterization and Identification of Microorganisms

Application Examples in Microbiology

Characterization and Differentiation of Microorganisms

Gram Type

G + CPercentage

Endospore Formation

Cell Storage Materials

Metabolically ReleasedCO2

Industrial Applications

Biomedical Applications

Identification

Antibiotic Susceptibility Testing

Reference Databases for the Identification of Microorganisms

Conclusion/Future Directions
Vibrational Spectroscopy in the Detection of Cancer
Authors: Dukor Rina K.
Published: September 2006

The sections in this article are

Introduction

Vibrational Spectroscopy – Sensitivity to Structures of Biological Molecules

Nucleic Acids

Proteins

Lipids

Carbohydrates

Cells and Tissues

Cell Biology

Cancer

Experimental Techniques

Histological Samples

IR

and
R
aman Sampling Techniques

Liquid Sampling

Solid Sampling

Macroscopic Sampling

IR
Transmission and Reflection

Fiber‐Optic Probes

R
aman Spectroscopy

Microscopic Sampling

Mid‐Infrared Synchrotron Radiation

Mid‐Infrared
FPA
Detection

CCD
Detection in
R
aman

Spectroscopic Sample

Applications

Breast

Cervix

Conclusions

Acknowledgments
Guidelines for the Development and Validation of Near‐Infrared Spectroscopic Methods in the Pharmaceutical Industry
Authors: Broad Neville , Graham Paul , Hailey Perry , Hardy Allison , Holland Steve , Hughes Stephen , Lee David , Prebble Ken , Salton Neale , Warren Paul , Leiper Ken
Published: September 2006

The sections in this article are

Preface

Introduction

Background and Purpose

Overview

Types of Near‐Infrared Procedures to be Validated

Validation Requirements

Equipment

Equipment Selection

Equipment Qualification

Design Qualification

Installation Qualification

Operational Qualification

Performance Qualification

Change Control

Hardware

Software

Glossary

References

Books

Useful Reference Journals

Useful Papers

Technical Guidelines for Qualitative Methods

Introduction to Qualitative Analysis

Feasibility Study

Sample Authentication, Collection and Measurement

Sample Measurement/Presentation

Measurement by Transmission

Liquids and Solutions

Solids

Measurement by Diffuse Reflection

Measurement by Transflection

Library Development

Define the Purpose

Selection of Samples/Spectra for Calibration Set

Display Data

Calibration Set Selection

Data Pre‐Processing/Transformation

Library Construction

Determination of Thresholds

Library Validation

Internal and External Validation

Internal

External

Specificity

Repeatability

Robustness

Routine Use

Out‐of‐Specification Results

Library Maintenance

Database

Material Groupings

New Materials Addition

Material “Library Group” Modification

Technical Guidelines for Quantitative Methods

Introduction to Quantitative Analysis

Feasibility Study

Sample Collection

Sample Scanning

Displaying and Checking Spectra

Reference Data

Sample Selection – Calibration and Calibration Test Sets

Data Pre‐Processing

Generation of Calibration Model

Validation of Calibration Model

Performance Verification

Accuracy Monitoring

Use of a Check Sample

Comparison with Reference Method

Maintenance of the Calibration Model

Method Transfer

Acknowledgments
Cephalic vascular anatomy in flamingos (Phoenicopterus ruber) based on novel vascular injection and computed tomographic imaging analyses
Authors: Holliday Casey M. , Ridgely Ryan C. , Balanoff Amy M. , Witmer Lawrence M.
Published: September 2006

Head vascular anatomy of the greater (or Caribbean) flamingo (Phoenicopterus ruber) is investigated and illustrated through the use of a differential contrast, dual vascular injection technique, and high‐resolution X‐ray computed tomography (CT), allowing arteries and veins to be differentiated radiographically. Vessels were digitally isolated with segmentation tools and reconstructed in 3D to facilitate topographical visualization of the cephalic vascular tree. Major vessels of the temporal, orbital, pharyngeal, and encephalic regions are described and illustrated, which confirm that the general pattern of avian cephalic vasculature is evolutionarily conservative. In addition to numerous arteriovenous vascular devices, a previously undescribed, large, bilateral, paralingual cavernous sinus that excavates a large bony fossa on the medial surface of the mandible was identified. Despite the otherwise conservative vascular pattern, this paralingual sinus was found only in species of flamingo and is not known otherwise in birds. The paralingual sinus remains functionally enigmatic, but a mechanical role in association with the peculiar lingual‐pumping mode of feeding in flamingos is perhaps the most likely hypothesis. Anat Rec Part A, 288A:1031–1041, 2006. © 2006 Wiley‐Liss, Inc.