Vibrational Spectroscopy at Electrified Interfaces
The Wiley Series on Electrocatalysis and Electrochemistry Series

Reviews the latest theory, techniques, and applications

Surface vibrational spectroscopy techniques probe the structure and composition of interfaces at the molecular level. Their versatility, coupled with their non-destructive nature, enables in-situ measurements of operating devices and the monitoring of interface-controlled processes under reactive conditions.

Vibrational Spectroscopy at Electrified Interfaces explores new and emerging applications of Raman, infrared, and non-linear optical spectroscopy for the study of charged interfaces. The book draws from hundreds of findings reported in the literature over the past decade. It features an internationally respected team of authors and editors, all experts in the field of vibrational spectroscopy at surfaces and interfaces. Content is divided into three parts:

• Part One, Nonlinear Vibrational Spectroscopy, explores properties of interfacial water, ions, and biomolecules at charged dielectric, metal oxide, and electronically conductive metal catalyst surfaces. In addition to offering plenty of practical examples, the chapters present the latest measurement and instrumental techniques.
• Part Two, Raman Spectroscopy, sets forth highly sensitive approaches for the detection of biomolecules at solid-liquid interfaces as well as the use of photon depolarization strategies to elucidate molecular orientation at surfaces.
• Part Three, IRRAS Spectroscopy (including PM-IRRAS), reports on wide-ranging systems—from small fuel molecules at well-defined surfaces to macromolecular complexes—that serve as the building blocks for functional interfaces in devices designed for chemical sensing and electric power generation.

The Wiley Series on Electrocatalysis and Electrochemistry is dedicated to reviewing important advances in the field, exploring how these advances affect industry. The series defines what we currently know and can do with our knowledge of electrocatalysis and electrochemistry as well as forecasts where we can expect the field to be in the future.

Preface to the Wiley Series on Electrocatalysis and Electrochemistry vii

Foreword ix
by Masatoshi Osawa

Preface xi

Contributors xiii

Part One Nonlinear Vibrational Spectroscopy

1. Water Hydrogen Bonding Dynamics at Charged Interfaces Observed with Ultrafast Nonlinear Vibrational Spectroscopy 3
Emily E. Fenn and Michael D. Fayer

2. SFG Studies of Oxide–Water Interfaces: Protonation States, Water Polar Orientations, and Comparison with Structure Results from X-Ray Scattering 48
Y. Ron Shen and Glenn A. Waychunas

3. Vibrational Sum Frequency Generation Spectroscopy of Interfacial Dynamics 85
Christopher M. Berg and Dana D. Dlott

4. Spectroscopy of Electrifi ed Interfaces with Broadband Sum Frequency Generation: From Electrocatalysis to Protein Foams 120
Björn Braunschweig, Prabuddha Mukherjee, Robert B. Kutz, Armin Rumpel, Kathrin
Engelhardt, Wolfgang Peukert, Dana D. Dlott, and Andrzej Wieckowski

Part Two Raman Spectroscopy

5. Surface-Enhanced Resonance Raman Scattering (SERRS) Studies of Electron-Transfer Redox-Active Protein Attached to Thiol-Modified Metal: Case of Cytochrome c 153
Agata Królikowska

6. Depolarization of Surface-Enhanced Raman Scattering Photons from a Small Number of Molecules on Metal Surfaces 220
Fumika Nagasawa, Mai Takase, Hideki Nabika, and Kei Murakoshi

Part Three IRRAS Spectroscopy (Including PM–IRRAS)

7. DFT and In Situ Infrared Studies on Adsorption and Oxidation of Glycine, l-Alanine, and l-Serine on Gold Electrodes 241
Andrea P. Sandoval, José Manuel Orts, Antonio Rodes, and Juan M. Feliu

8. Composition, Structure, and Reaction Dynamics at Electrode–Electrolyte Interfaces Using Infrared Spectroscopy 266
Angel Cuesta

9. Vibrational Stark Effect at Halide Precovered Cu(100) Electrodes 307
Melanie Röefzaad, Duc Thanh Pham, and Klaus Wandelt

10. Vibrational Spectroscopy of the Ionomer–Catalyst Interface 327
Ian Kendrick, Jonathan Doan, and Eugene S. Smotkin

11. In Situ PM–IRRAS Studies of Biomimetic Membranes Supported at Gold Electrode Surfaces 345
Annia H. Kycia, ZhangFei Su, Christa L. Brosseau, and Jacek Lipkowski

Index 418

ANDRZEJ WIECKOWSKI, PhD, is Emeritus Professor of Chemistry at the University of Illinois and the North American Editor for Electrochimica Acta. His research focused on electrode surface structure in relation to electrocatalysis, molecular-level studies of surface oxidation and reduction processes, and surface motional behavior in electrocatalysis.

CAROL KORZENIEWSKI, PhD, is Professor of Chemistry at Texas Tech University. Her research, supported by the U. S. National Science Foundation, Department of Energy, and Department of Defense, centers on the use of vibrational spectroscopy to probe interfacial processes in electrochemistry.

BJÖRN BRAUNSCHWEIG, PhD, is a Postdoctoral Research Associate at the University of Erlangen-Nuremberg and was a recipient of the Feodor Lynen Research Fellowship of the Alexander von Humboldt Foundation. His junior research group focuses on the nonlinear optical spectroscopy of charged interfaces.