Condensed-Phase Molecular Spectroscopy and Photophysics

An introduction to one of the fundamental tools in chemical research—spectroscopy and photophysics in condensed-phase and extended systems

Condensed-Phase Molecular Spectroscopy and Photophysics comprehensively covers radiation-matter interactions for molecules in condensed phases along with metallic and semiconductor nanostructures, examining optical processes in extended systems such as metals, semiconductors, and conducting polymers and addressing the unique optical properties of nanoscale systems.

The text differs from others through its emphasis on the molecule-environment interactions that strongly influence spectra in condensed phases, including spectroscopy and photophysics of molecular aggregates, molecular solids, and metals and semiconductors, as well as more modern topics such as two-dimensional and single-molecule spectroscopy.

To aid in reader comprehension, the text includes case studies and illustrated examples. An online manual with solutions to the problems in the book is available to all readers on a companion website.

Condensed-Phase Molecular Spectroscopy and Photophysics begins with an introduction to quantum mechanics that sets a solid foundation for understanding the text’s subsequent topics, including:

• Electromagnetic radiation and radiation-matter interactions, molecular vibrations and infrared spectroscopy, and electronic spectroscopy
• Photophysical processes and light scattering, nonlinear and pump-probe spectroscopies, and electron transfer processes
• Basic rotational spectroscopy and statistical mechanics, Raman scattering, 2D and single-molecule spectroscopies, and time-domain pictures of steady-state spectroscopies
• Time-independent quantum mechanics, statistical mechanics, group theory, radiation-matter interactions, and system-bath interactions
• Atomic spectroscopy, photophysical processes, light scattering, nonlinear and pump-probe spectroscopies, two-dimensional spectroscopies, and metals and plasmons

Written for researchers and upper-level undergraduate and graduate courses in physical and materials chemistry, Condensed-Phase Molecular Spectroscopy and Photophysics is a valuable learning resource that is uniquely designed to equip readers to solve a broad array of current problems and challenges in the vast field of chemistry.

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 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

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