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Surface–Enhanced Vibrational Spectroscopy

  • ID: 2178023
  • Book
  • March 2006
  • Region: Global
  • 260 Pages
  • John Wiley and Sons Ltd
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This book discusses two of the many enhanced optical phenomena in surface–enhanced spectroscopy: surface–enhanced Raman scattering (SERS) and surface–enhanced infrared absorption (SEIRA). Together, these form a new branch of vibrational spectroscopy Surface–Enhanced Vibrational Spectroscopy (SEVS). SEVS deals with the enhanced spectra of molecules on specially fabricated metal nanostructures with the ability to support surface plasmons and to enhance optical signals.  The great advantage of vibrational spectroscopy is that it provides the fingerprint of any molecular system; with a large amount of vibrational assignment data for gas, liquid, solid, and, most relevant to SEVS, surface complex systems widely available in the literature. SEVS is an extremely powerful addition to surface–sensitive and single molecule spectroscopies (SMS).

The book begins with a review of the vibrating molecule and the origin of infrared and Raman spectra.

Chapter 2 contains brief discussions on the absorption and scattering of light by metallic nanoparticles, the fabrication of nanostructures, and the selection of the appropriate experimental conditions for SERS and SEIRA.

Chapter 3 is dedicated to SERS as a surface plasmon assisted spectroscopy and includes discussion of the most rudimentary models that provide guidance for the experimentalist. 

Chapter 4 examines the role in observed SERS spectra of molecule nanostructure interactions, or chemical effects.

Chapter 5 is dedicated to demonstrating that the SERS effect is functional for all molecular types.

Chapter 6 presents an overview of SERS applications.

The concluding chapter describes surface–enhanced infrared absorption (SEIRA) and its applications.

Each chapter contains extensive citation to help the user, and to make the book a useful reference. A glossary is also included to help provide common terminology for those working in the multiple disciplines touched by SERS (chemistry, solid state physics, optics and electrodynamics). A comprehensive reference database of almost 3000 references from the literature from 1980 to 2004 with a listing of references by keyword is provided on [external URL]

The book is intended to serve as an introduction for scientists, technologists, and students who may use some aspect of surface–enhanced vibrational spectroscopy in their work. It has been designed to provide a general introduction to concepts and techniques, rather than a strong theoretical or experimental background. Given the multidisciplinary nature of the phenomenon and its applications, the book will be a practical help for anyone in chemistry, physics, biomedical research, or materials science in need of ultrasensitive chemical analysis with high information content, and high spatial resolution.

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1. Theory of Molecular Vibrations. The Origin of Infrared and Raman Spectra.

1.1 Electronic, Vibrational, Rotational and Translational Energy.

1.2 Separation of Nuclear and Electronic Motions.

1.3 Vibrations in Polyatomic Molecules.

1.4 Equilibrium Properties. Dipole Moment and Polarizability.

1.5 Fundamental Vibrational Transitions in the Infrared and Raman Regions.

1.6 Symmetry of Normal Modes and Vibrational States.

1.7 Selection Rules.

1.8 The Example of ab initio Computation of the Raman and Infrared Spectra.

1.9 Vibrational Intensities.

1.10 Definition of Cross–Section.

1.11 The Units of Energy and Force Constants.


2. The Interaction of Light with Nanoscopic Metal Particles and Molecules on Smooth Reflecting Surfaces.

2.1 Electric Permittivity and Refractive Index.

2.2 Propagation of Electromagnetic Waves and the Optical Properties of Materials.

2.3 Scattering and Absorption by Nanoscopic Particles.

2.4 Reflection Absorption Infrared Spectroscopy on Smooth Metal Surfaces.


3. Surface–Enhanced Raman Scattering (SERS).

3.1 Electromagnetic Enhancement Mechanism.


4. Chemical Effects and the SERS Spectrum.

4.1 Physical and Chemical Adsorption.

4.2 SERS/SERRS of Physically Adsorbed Molecules.

4.3 SERS of Chemically Adsorbed Molecules without Electronic Resonance Excitation.

4.4 SERS of Chemically Adsorbed Molecules with Charge Transfer Excitation.

4.5 Metal Molecule or Molecule Metal Charge Transfer.

4.6 SERRS from a Surface Complex.


5. Is SERS Molecule Specific?


6. SERS/SERRS, the Analytical Tool.

6.1 Average SERS on Metal Colloids. Preparation and Properties.

6.2 Metal Colloids. The Background SERS.

6.3 Metal Colloids. Maximizing the Average SERS in Solution.

6.4 Average SERS on Metal Island Films.

6.5 Average SERS on Rough Electrodes.

6.6 Ultrasensitive SERS Analysis and Single Molecule Detection.

6.7 Uniqueness of Ultrasensitive Chemical Analysis. The Moving Target.

6.8 Applications and Outlook.


7. Surface–Enhanced Infrared Spectroscopy.

7.1 Overview.

7.2 Theoretical Models for SEIRA.

7.3 SEIRA–Active Substrates.

7.4 Interpretation of the Observed SEIRA Spectra.

7.5 Applications of SEIRA.



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Ricardo Aroca
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