Condensed-Phase Molecular Spectroscopy and Photophysics

Anne Myers Kelley, PhD is a founding faculty of the Department of Chemistry and Biochemistry at the University of California, Merced. Her primary research area is resonance Raman spectroscopy, linear and nonlinear, but she has also worked in several other areas of spectroscopy including single-molecule and line-narrowed fluorescence, four-wave mixing, and time-resolved methods.

• Preface to Second EditionPreface to First EditionAbout the Companion WebsiteI. BACKGROUND1. Time-Independent Quantum Mechanics1.1. states, operators, and representations1.2. eigenvalue problems and the Schrödinger equation1.3. expectation values, uncertainty relations1.4. particle in a box1.5. harmonic oscillator1.6. the rigid rotator and angular momentum1.7. the hydrogen atom1.8. approximation methods1.9. electron spin1.10. Born-Oppenheimer approximation1.11. molecular orbitals1.12. energies and time scales, separation of motions2. Classical Description of Electromagnetic Radiation2.1. Maxwell’s equations, plane waves, electric and magnetic fields, polarization2.2. Fourier transform relationships between time and frequency2.3. blackbody radiation2.4. light sources for spectroscopy3. Statistical mechanics3.1. the partition function3.2. the Boltzmann distribution4. Group theory 4.1. qualitative aspects of molecular symmetry4.2. introductory group theory4.3. finding the symmetries of vibrational modes of a certain type4.4. finding the symmetries of all vibrational modesII. FUNDAMENTALS OF SPECTROSCOPY5. Radiation-Matter Interactions5.1. the time-dependent Schrödinger equation5.2. time-dependent perturbation theory5.3. interaction of matter with the classical radiation field5.4. quantum mechanical description of radiation5.5. interaction of matter with the quantized radiation field6. Absorption and Emission of Light by Matter6.1. Einstein coefficients for absorption and emission6.2. other measures of absorption strength (absorption cross-section, Beer-Lambert Law)6.3. radiative lifetimes6.4. oscillator strengths6.5. local fields7. System-Bath Interactions7.1. phenomenological treatment of relaxation and lineshapes7.2. the density matrix7.3. density matrix methods in spectroscopy7.4. exact density matrix solution for a 2-level system8. Atomic Spectroscopy8.1. electron configurations8.2. addition of angular momenta8.3. term symbols8.4. angular momentum coupling schemes8.5. spin-orbit coupling8.6. energies and selection rules8.7. Zeeman effect8.8. hyperfine splitting9. Rotational Spectroscopy9.1. rotational transitions of diatomic molecules9.2. rotational spectroscopy of polyatomic molecules—symmetric, near-symmetric, and asymmetric tops10. Molecular Vibrations and Infrared Spectroscopy10.1. vibrational and rovibrational transitions10.2. diatomic vibrations10.3. anharmonicity10.4. polyatomic molecular vibrations; normal modes10.5. vibration-rotation interactions10.6. symmetry considerations10.7. isotopic shifts10.8. solvent effects on vibrational spectra11. Electronic Spectroscopy11.1. electronic transitions11.2. spin and orbital selection rules11.3. vibronic structure11.4. vibronic coupling11.5. the Jahn-Teller effect11.6. considerations in large molecules11.7. solvent effects on electronic spectra12. Photophysical Processes12.1. Jablonski diagrams12.2. quantum yields and lifetimes12.3. Fermi’s Golden Rule for radiationless transitions12.4. internal conversion and intersystem crossing12.5. bright state-dark state coupling and intramolecular vibrational relaxation12.6. energy transfer12.7. polarization and molecular reorientation in solution13. Light Scattering13.1. Rayleigh scattering from particles13.2. classical treatment of molecular Raman and Rayleigh scattering13.3. quantum mechanical treatment of molecular Raman and Rayleigh scattering13.4. nonresonant Raman scattering13.5. symmetry considerations and depolarization ratios in Raman scattering13.6. resonance Raman spectroscopyIII. ADVANCED AND SPECIALIZED TOPICS IN SPECTROSCOPY14. Nonlinear and Pump-Probe Spectroscopies14.1. linear and nonlinear susceptibilities14.2. multiphoton absorption14.3. pump-probe spectroscopy: transient absorption and stimulated emission14.4. vibrational oscillations and impulsive stimulated scattering14.5. second harmonic and sum frequency generation14.6. four-wave mixing14.7. photon echoes14.8. hyper-Raman scattering14.9. broadband stimulated Raman scattering15. Two-dimensional spectroscopies15.1. the basics of two-dimensional spectroscopy15.2. Fourier transform spectroscopy15.3. implementation of Fourier transform 2D spectroscopy16. Electron Transfer Processes16.1. charge-transfer transitions16.2. Marcus theory16.3. spectroscopy of anions and cations17. Collections of Molecules17.1. van der Waals molecules17.2. dimers and aggregates17.3. localized and delocalized excited states17.4. conjugated polymers18. Metals and Plasmons18.1. dielectric function of a metal18.2. plasmons18.3. spectroscopy of metal nanoparticles18.4. surface-enhanced Raman and fluorescence19. Crystals 19.1. crystal lattices19.2. phonons in crystals19.3. infrared and Raman spectra19.4. phonons in nanocrystals20. Electronic Spectroscopy of Semiconductors20.1. band structure20.2. direct and indirect transitions20.3. excitons20.4. defects20.5. semiconductor nanocrystals21. Single-molecule spectroscopy21.1. detection of single-molecule signals21.2. verification of single-molecule signals21.3. frequency selection21.4. spatial selection using far-field optics21.5. spatial selection using near-field optics21.6. what is learned from studying one molecule at a time?22. Time-domain treatment of steady-state spectroscopies22.1. time correlation function approach to IR and Raman lineshapes22.2. time-dependent wavepacket picture of electronic spectroscopy22.3. time-dependent wavepacket picture of resonance Raman intensitiesAPPENDICESA. Physical constants, unit systems and conversion factorsB. Miscellaneous mathematics reviewC. Matrices and determinantsD. Character tables for point groupsE. Fourier transformsIndex