Condensed-Phase Molecular Spectroscopy and Photophysics

Preface to Second Edition Preface to First Edition About the Companion Website I. BACKGROUND 1. Time-Independent Quantum Mechanics 1.1. states, operators, and representations 1.2. eigenvalue problems and the Schrödinger equation 1.3. expectation values, uncertainty relations 1.4. particle in a box 1.5. harmonic oscillator 1.6. the rigid rotator and angular momentum 1.7. the hydrogen atom 1.8. approximation methods 1.9. electron spin 1.10. Born-Oppenheimer approximation 1.11. molecular orbitals 1.12. energies and time scales, separation of motions 2. Classical Description of Electromagnetic Radiation 2.1. Maxwell’s equations, plane waves, electric and magnetic fields, polarization 2.2. Fourier transform relationships between time and frequency 2.3. blackbody radiation 2.4. light sources for spectroscopy 3. Statistical mechanics 3.1. the partition function 3.2. the Boltzmann distribution 4. Group theory 4.1. qualitative aspects of molecular symmetry 4.2. introductory group theory 4.3. finding the symmetries of vibrational modes of a certain type 4.4. finding the symmetries of all vibrational modes II. FUNDAMENTALS OF SPECTROSCOPY 5. Radiation-Matter Interactions 5.1. the time-dependent Schrödinger equation 5.2. time-dependent perturbation theory 5.3. interaction of matter with the classical radiation field 5.4. quantum mechanical description of radiation 5.5. interaction of matter with the quantized radiation field 6. Absorption and Emission of Light by Matter 6.1. Einstein coefficients for absorption and emission 6.2. other measures of absorption strength (absorption cross-section, Beer-Lambert Law) 6.3. radiative lifetimes 6.4. oscillator strengths 6.5. local fields 7. System-Bath Interactions 7.1. phenomenological treatment of relaxation and lineshapes 7.2. the density matrix 7.3. density matrix methods in spectroscopy 7.4. exact density matrix solution for a 2-level system 8. Atomic Spectroscopy 8.1. electron configurations 8.2. addition of angular momenta 8.3. term symbols 8.4. angular momentum coupling schemes 8.5. spin-orbit coupling 8.6. energies and selection rules 8.7. Zeeman effect 8.8. hyperfine splitting 9. Rotational Spectroscopy 9.1. rotational transitions of diatomic molecules 9.2. rotational spectroscopy of polyatomic molecules—symmetric, near-symmetric, and asymmetric tops 10. Molecular Vibrations and Infrared Spectroscopy 10.1. vibrational and rovibrational transitions 10.2. diatomic vibrations 10.3. anharmonicity 10.4. polyatomic molecular vibrations; normal modes 10.5. vibration-rotation interactions 10.6. symmetry considerations 10.7. isotopic shifts 10.8. solvent effects on vibrational spectra 11. Electronic Spectroscopy 11.1. electronic transitions 11.2. spin and orbital selection rules 11.3. vibronic structure 11.4. vibronic coupling 11.5. the Jahn-Teller effect 11.6. considerations in large molecules 11.7. solvent effects on electronic spectra 12. Photophysical Processes 12.1. Jablonski diagrams 12.2. quantum yields and lifetimes 12.3. Fermi’s Golden Rule for radiationless transitions 12.4. internal conversion and intersystem crossing 12.5. bright state-dark state coupling and intramolecular vibrational relaxation 12.6. energy transfer 12.7. polarization and molecular reorientation in solution 13. Light Scattering 13.1. Rayleigh scattering from particles 13.2. classical treatment of molecular Raman and Rayleigh scattering 13.3. quantum mechanical treatment of molecular Raman and Rayleigh scattering 13.4. nonresonant Raman scattering 13.5. symmetry considerations and depolarization ratios in Raman scattering 13.6. resonance Raman spectroscopy III. ADVANCED AND SPECIALIZED TOPICS IN SPECTROSCOPY 14. Nonlinear and Pump-Probe Spectroscopies 14.1. linear and nonlinear susceptibilities 14.2. multiphoton absorption 14.3. pump-probe spectroscopy: transient absorption and stimulated emission 14.4. vibrational oscillations and impulsive stimulated scattering 14.5. second harmonic and sum frequency generation 14.6. four-wave mixing 14.7. photon echoes 14.8. hyper-Raman scattering 14.9. broadband stimulated Raman scattering 15. Two-dimensional spectroscopies 15.1. the basics of two-dimensional spectroscopy 15.2. Fourier transform spectroscopy 15.3. implementation of Fourier transform 2D spectroscopy 16. Electron Transfer Processes 16.1. charge-transfer transitions 16.2. Marcus theory 16.3. spectroscopy of anions and cations 17. Collections of Molecules 17.1. van der Waals molecules 17.2. dimers and aggregates 17.3. localized and delocalized excited states 17.4. conjugated polymers 18. Metals and Plasmons 18.1. dielectric function of a metal 18.2. plasmons 18.3. spectroscopy of metal nanoparticles 18.4. surface-enhanced Raman and fluorescence 19. Crystals 19.1. crystal lattices 19.2. phonons in crystals 19.3. infrared and Raman spectra 19.4. phonons in nanocrystals 20. Electronic Spectroscopy of Semiconductors 20.1. band structure 20.2. direct and indirect transitions 20.3. excitons 20.4. defects 20.5. semiconductor nanocrystals 21. Single-molecule spectroscopy 21.1. detection of single-molecule signals 21.2. verification of single-molecule signals 21.3. frequency selection 21.4. spatial selection using far-field optics 21.5. spatial selection using near-field optics 21.6. what is learned from studying one molecule at a time? 22. Time-domain treatment of steady-state spectroscopies 22.1. time correlation function approach to IR and Raman lineshapes 22.2. time-dependent wavepacket picture of electronic spectroscopy 22.3. time-dependent wavepacket picture of resonance Raman intensities APPENDICES A. Physical constants, unit systems and conversion factors B. Miscellaneous mathematics review C. Matrices and determinants D. Character tables for point groups E. Fourier transforms Index