The advent of laser-based sources of ultrafast infrared pulses has extended the study of very fast molecular dynamics to the observation of processes manifested through their effects on the vibrations of molecules. In addition, non-linear infrared spectroscopic techniques make it possible to examine intra- and intermolecular interactions and how such interactions evolve on very fast time scales, but also in some instances on very slow time scales. Ultrafast Infrared Vibrational Spectroscopy is an advanced overview of the field of ultrafast infrared vibrational spectroscopy based on the scientific research of the leading figures in the field. The book discusses experimental and theoretical topics reflecting the latest accomplishments and understanding of ultrafast infrared vibrational spectroscopy. Each chapter provides background, details of methods, and explication of a topic of current research interest. Experimental and theoretical studies cover topics as diverse as the dynamics of water and the dynamics and structure of biological molecules. Methods covered include vibrational echo chemical exchange spectroscopy, IR-Raman spectroscopy, time resolved sum frequency generation, and 2D IR spectroscopy. Edited by a recognized leader in the field and with contributions from top researchers, including experimentalists and theoreticians, this book presents the latest research methods and results. It will serve as an excellent resource for those new to the field, experts in the field, and individuals who want to gain an understanding of particular methods and research topics.

A description of procedures for probing bond activation, H-bonded systems, molecular dynamical mechanisms, vibrational dephasing, simple liquids, and proteins and energy flow effects using ultrafast vibrational spectroscopy experiments. It discusses experimental and theoretical methods of ultrafast infrared and Raman measurements.

A description of procedures for probing bond activation, H-bonded systems, molecular dynamical mechanisms, vibrational dephasing, simple liquids, and proteins and energy flow effects using ultrafast vibrational spectroscopy experiments. It discusses experimental and theoretical methods of ultrafast infrared and Raman measurements.

Chemistry

Ultrafast infrared 2D-IR vibrational echo experiments were extended experimentally and theoretically. Detailed studies of water dynamics were performed and compared to MD simulations. 2D-IR vibrational echo chemical exchange experiments were used to study the formation and dissociation kinetics of eight solute-solvent complexes, and the results were related to the enthalpies of formation. MD simulations of the chemical exchange were performed for the phenol-benzene complex and found to be in good agreement with the data. Chemical exchange experiments were used to measure the rate of gauche-trans orientational isomerization about a carbon-carbon single bond. The dynamics of molecules in the first solvation shell of solutes in mixed solvents were studied, and the time dependent solvent compositional fluctuations about solutes were elucidated. A detailed time dependent diagrammatic perturbation theory of the 2D-IR vibrational echo chemical exchange experiment including spectral diffusion, orientational relaxation, and vibrational relaxation was developed. An important new theoretical method for determining the dynamics from 2D-IR vibrational echo experiments was developed and demonstrated.

2D infrared (IR) spectroscopy is a cutting-edge technique, with applications in subjects as diverse as the energy sciences, biophysics and physical chemistry. This book introduces the essential concepts of 2D IR spectroscopy step-by-step to build an intuitive and in-depth understanding of the method. This unique book introduces the mathematical formalism in a simple manner, examines the design considerations for implementing the methods in the laboratory, and contains working computer code to simulate 2D IR spectra and exercises to illustrate involved concepts. Readers will learn how to accurately interpret 2D IR spectra, design their own spectrometer and invent their own pulse sequences. It is an excellent starting point for graduate students and researchers new to this exciting field. Computer codes and answers to the exercises can be downloaded from the authors' website, available at www.cambridge.org/9781107000056.

This unique volume presents a comprehensive but accessible introduction to the field of ultrafast two-dimension infrared (2D IR) vibrational echo spectroscopy based on the pioneering work of Professor Michael D Fayer, Department of Chemistry, Stanford University, USA. It contains in one place a qualitative introduction to the field of 2D IR spectroscopy and a comprehensive set of scientific papers that underlie the qualitative discussion. The introductory material contains several detailed illustrations, and is based on the Centenary Lecture at the Indian Institute of Science given by Professor Fayer July 16, 2008 as part of the celebration of the 100th anniversary of the founding of IIS in Bangalore, India. The second part of the volume contains reprints of Fayer's relevant papers. The compilation will be very useful because it presents the historical background, motivation, methodology, and experimental results at a level that is accessible to the non-expert. The reprints of the scientific papers, from review articles to detailed theoretical papers, provide rigorous supporting material so that the reader can delve as deeply as desired into the subject.