Concepts and methods of 2d infrared spectroscopy

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.

Author Notes

Peter Hamm is a Professor at the Institute of Physical Chemistry, University of Zurich.
Martin Zanni is Meloche-Bascom Professor in the Department of Chemistry, University of Wisconsin-Madison.
They specialize in using 2D IR spectroscopy to study molecular structures and dynamics.

1 Introduction	p. 1
1.1 Studying molecular structure with 2D IR spectroscopy	p. 3
1.2 Structural distributions and inhomogeneous broadening	p. 10
1.3 Studying structural dynamics with 2D IR spectroscopy	p. 12
1.4 Time domain 2D IR spectroscopy	p. 14
Exercises	p. 16
2 Designing multiple pulse experiments	p. 18
2.1 Eigenstates, coherences and the emitted field	p. 18
2.2 Bloch vectors and molecular ensembles	p. 23
2.3 Bloch vectors are a graphical representation of the density matrix	p. 27
2.4 Multiple pathways visualized with Feynman diagrams	p. 31
2.5 What is absorption?	p. 37
2.6 Designing multi-pulse experiments	p. 38
2.7 Selecting pathways by phase matching	p. 42
2.8 Selecting pathways by phase cycling	p. 44
2.9 Double sided Feynman diagrams: Rules	p. 46
Exercises	p. 47
3 Mukamelian or perturbative expansion of the density matrix	p. 48
3.1 Density matrix	p. 48
3.2 Time dependent perturbation theory	p. 52
Exercises	p. 60
4 Basics of 2D IR spectroscopy	p. 61
4.1 Linear spectroscopy	p. 61
4.2 Third-order response functions	p. 65
4.3 Time domain 2D IR spectroscopy	p. 69
4.4 Frequency domain 2D IR spectroscopy	p. 82
4.5 Transient pump-probe spectroscopy	p. 84
Exercises	p. 86
5 Polarization control	p. 88
5.1 Using polarization to manipulate the molecular response	p. 88
5.2 Diagonal peak, no rotations	p. 92
5.3 Cross-peaks and orientations of coupled transition dipoles	p. 93
5.4 Combining pulse polarizations: Eliminating diagonal peaks	p. 99
5.5 Including (or excluding) rotational motions	p. 100
5.6 Polarization conditions for higher-order pulse sequences	p. 106
Exercises	p. 108
6 Molecular couplings	p. 109
6.1 Vibrational excitons	p. 109
6.2 Spectroscopy of a coupled dimer	p. 114
6.3 Extended excitons in regular structures	p. 120
6.4 Isotope labeling	p. 128
6.5 Local mode transition dipoles	p. 133
6.6 Calculation of coupling constants	p. 134
6.7 Local versus normal modes	p. 137
6.8 Fermi resonance	p. 140
Exercises	p. 142
7 2D IR lineshapes	p. 145
7.1 Microscopic theory of dephasing	p. 145
7.2 Correlation functions	p. 149
7.3 Homogeneous and inhomogeneous dynamics	p. 152
7.4 Nonlinear response	p. 155
7.5 Photon echo peak shift experiments	p. 161
Exercises	p. 164
8 Dynamic cross-peaks	p. 166
8.1 Population transfer	p. 166
8.2 Dynamic response functions	p. 172
8.3 Chemical exchange	p. 174
9 Experimental designs, data collection and processing	p. 176
9.1 Frequency domain spectrometer designs	p. 176
9.2 Experimental considerations for impulsive spectrometer designs	p. 180
9.3 Capabilities made possible by phase control	p. 191
9.4 Phase control devices	p. 197
9.5 Data collection and data workup	p. 201
9.6 Experimental issues common to all methods	p. 214
Exercises	p. 216
10 Simple simulation strategies	p. 217
10.1 2D lineshapes: Spectral diffusion of water	p. 217
10.2 Molecular couplings by ab initio calculations	p. 226
10.3 2D spectra using an exciton approach	p. 229
Exercises	p. 232
11 Pulse sequence design: Some examples	p. 233
11.1 Two-quantum pulse sequence	p. 233
11.2 Rephased 2Q pulse sequence: Fifth-order spectroscopy	p. 236
11.3 3D IR spectroscopy	p. 239
11.4 Transient 2D IR spectroscopy	p. 243
11.5 Enhancement of 2D IR spectra through coherent control	p. 245
11.6 Mixed IR-Vis spectroscopies	p. 247
11.7 Some of our dream experiments	p. 249
Exercises	p. 252
Appendix A Fourier transformation	p. 254
A.1 Sampling theorem, aliasing and under-sampling	p. 256
A.2 Discrete Fourier transformation	p. 257
Appendix B The ladder operator formalism	p. 260
Appendix C Units and physical constants	p. 262
C.1 Physical constants	p. 262
C.2 Units of common physical quantities	p. 262
C.3 Emitted field E (3) sig	p. 263
Appendix D Legendre polynomials and spherical harmonics	p. 265
Appendix E Recommended reading	p. 267
References	p. 269
Index	p. 281

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