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Concepts and Methods of 2D Infrared Spectroscopy

Book Description

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.

Table of Contents

  1. Cover
  2. Half Title
  3. Title Page
  4. Copyright
  5. Dedication
  6. Contents
  7. 1. Introduction
    1. 1.1 Studying molecular structure with 2D IR spectroscopy
    2. 1.2 Structural distributions and inhomogeneous broadening
    3. 1.3 Studying structural dynamics with 2D IR spectroscopy
    4. 1.4 Time domain 2D IR spectroscopy
    5. Exercises
  8. 2. Designing multiple pulse experiments
    1. 2.1 Eigenstates, coherences and the emitted field
    2. 2.2 Bloch vectors and molecular ensembles
    3. 2.3 Bloch vectors are a graphical representation of the density matrix
    4. 2.4 Multiple pathways visualized with Feynman diagrams
    5. 2.5 What is absorption?
    6. 2.6 Designing multi-pulse experiments
    7. 2.7 Selecting pathways by phase matching
    8. 2.8 Selecting pathways by phase cycling
    9. 2.9 Double sided Feynman diagrams: Rules
    10. Exercises
  9. 3. Mukamelian or perturbative expansion of the density matrix
    1. 3.1 Density matrix
    2. 3.2 Time dependent perturbation theory
    3. Exercises
  10. 4. Basics of 2D IR spectroscopy
    1. 4.1 Linear spectroscopy
    2. 4.2 Third-order response functions
    3. 4.3 Time domain 2D IR spectroscopy
    4. 4.4 Frequency domain 2D IR spectroscopy
    5. 4.5 Transient pump–probe spectroscopy
    6. Exercises
  11. 5. Polarization control
    1. 5.1 Using polarization to manipulate the molecular response
    2. 5.2 Diagonal peak, no rotations
    3. 5.3 Cross-peaks and orientations of coupled transition dipoles
    4. 5.4 Combining pulse polarizations: Eliminating diagonal peaks
    5. 5.5 Including (or excluding) rotational motions
    6. 5.6 Polarization conditions for higher-order pulse sequences
    7. Exercises
  12. 6. Molecular couplings
    1. 6.1 Vibrational excitons
    2. 6.2 Spectroscopy of a coupled dimer
    3. 6.3 Extended excitons in regular structures
    4. 6.4 Isotope labeling
    5. 6.5 Local mode transition dipoles
    6. 6.6 Calculation of coupling constants
    7. 6.7 Local versus normal modes
    8. 6.8 Fermi resonance
    9. Exercises
  13. 7. 2D IR lineshapes
    1. 7.1 Microscopic theory of dephasing
    2. 7.2 Correlation functions
    3. 7.3 Homogeneous and inhomogeneous dynamics
    4. 7.4 Nonlinear response
    5. 7.5 Photon echo peak shift experiments
    6. Exercises
  14. 8. Dynamic cross-peaks
    1. 8.1 Population transfer
    2. 8.2 Dynamic response functions
    3. 8.3 Chemical exchange
  15. 9. Experimental designs, data collection and processing
    1. 9.1 Frequency domain spectrometer designs
    2. 9.2 Experimental considerations for impulsive spectrometer designs
    3. 9.3 Capabilities made possible by phase control
    4. 9.4 Phase control devices
    5. 9.5 Data collection and data workup
    6. 9.6 Experimental issues common to all methods
    7. Exercises
  16. 10. Simple simulation strategies
    1. 10.1 2D lineshapes: Spectral diffusion of water
    2. 10.2 Molecular couplings by ab initio calculations
    3. 10.3 2D spectra using an exciton approach
    4. Exercises
  17. 11. Pulse sequence design: Some examples
    1. 11.1 Two-quantum pulse sequence
    2. 11.2 Rephased 2Q pulse sequence: Fifth-order spectroscopy
    3. 11.3 3D IR spectroscopy
    4. 11.4 Transient 2D IR spectroscopy
    5. 11.5 Enhancement of 2D IR spectra through coherent control
    6. 11.6 Mixed IR–Vis spectroscopies
    7. 11.7 Some of our dream experiments
    8. Exercises
  18. Appendix A Fourier transformation
    1. A.1 Sampling theorem, aliasing and under-sampling
    2. A.2 Discrete Fourier transformation
  19. Appendix B The ladder operator formalism
  20. Appendix C Units and physical constants
    1. C.1 Physical constants
    2. C.2 Units of common physical quantities
    3. C.3 Emitted field E(3)sig
  21. Appendix D Legendre polynomials and spherical harmonics
  22. Appendix E Recommended reading
  23. References
  24. Index