Molecular Spectroscopy

This textbook offers an introduction to the foundations of spectroscopic methods and provides a bridge between basic concepts and experimental applications in fields as diverse as materials science, biology, solar energy conversion, and environmental science. The author emphasizes the use of time-dependent theory to link the spectral response in the frequency domain to the behavior of molecules in the time domain, strengthened by two brand new chapters on nonlinear optical spectroscopy and time-resolved spectroscopy. Theoretical underpinnings are presented to the extent necessary for readers to understand how to apply spectroscopic tools to their own interests.

Introduction and ReviewHistorical PerspectiveDefinitions, Derivations and DiscoveryReview of Quantum MechanicsApproximate Solutions to the Schrödinger Equation: Variation and Perturbation TheoryStatistical MechanicsSummaryProblemsBibliography The Nature of Electromagnetic RadiationIntroductionThe Classical Description of Electromagnetic RadiationPropagation of Light in MatterQuantum Mechanical Aspects of Light SummaryProblemsBibliography Electric and Magnetic Properties of Molecules and Bulk MatterIntroductionElectric Properties of MoleculesElectric Properties of Bulk MatterMagnetic Properties of MatterSummary ProblemsBibliography Time-dependent Perturbation Theory of SpectroscopyIntroduction: Time Dependence in Quantum MechanicsTime-Dependent Perturbation TheoryRate Expression for EmissionPerturbation Theory Calculation of PolarizabilityQuantum Mechanical Expression for Emission RateTime Dependence of the Density MatrixSummaryProblemsBibliography The Time-Dependent Approach to SpectroscopyIntroductionTime-Correlation Functions and Spectra as Fourier-Transform PairsThe Properties of Time-Correlation Functions and Spectral LineshapesThe Fluctuation Dissipation TheoremRotational Correlation Functions and Pure Rotational SpectraReorientational Spectroscopy of Liquids: Single-Molecule and Collective DynamicsVibration-Rotation SpectraSpectral MomentsSummaryProblemsBibliography Experimental Consideration: Absorption: Emission, and ScatteringIntroductionEinstein A and B Coefficients for Absorption and EmissionAbsorption and Stimulated EmissionElectronic Absorption and Emission SpectroscopyMeasurement of Light Scattering: The Raman and Rayleigh EffectsSpectral LineshapesSummaryProblemsBibliography Atomic SpectroscopyIntroductionGood Quantum Numbers and Not So Good Quantum NumbersSelection Rules for Atomic Absorption and EmissionThe Effect of External FieldsAtomic Lasers and The Principles of Laser EmissionSummary ProblemsBibliography Rotational SpectroscopyIntroductionEnergy Levels for Free Rigid RotorsAngular Momentum Coupling in Non-1S Electronic StatesNuclear Statistics and the J states of Homonuclear DiatomicsRotational Absorption and Emission SpectroscopyRotational Raman SpectroscopyCorrections to the Rigid-Rotor ApproximationInternal RotationSummaryProblemsBibliography Vibrational Spectroscopy of Diatomic MoleculesIntroductionThe Born-Oppenheimer Approximation and Its ConsequencesThe Harmonic Oscillator ModelSelection Rules for Vibrational TransitionsBeyond the Rigid-Rotor Harmonic Oscillator ApproximationSummaryProblemsBibliography Vibrational Spectroscopy of PolyatomicsIntroductionNormal Modes of Vibration Quantum Mechanics of Polyatomic Vibrations Group Theoretical Treatment of VibrationsSelection Rules for Infrared Absorption and Raman Scattering: Group Theoretical Prediction of ActivityRotational StructureAnharmonicitySelection Rules at Work: BenzeneSolvent Effects on Infrared SpectraSummaryProblemsBibliography Electronic SpectroscopyIntroductionDiatomic Molecules: Electronic State and Selection RulesVibrational Structure in Electronic Spectra and DiatomicsBorn-Oppenheimer Breakdown in Diatomic MoleculesPolyatomic Molecules: Electronic States and Selection RulesTransition Metal Complexes: Forbidden Transitions and the Jahn-Teller EffectEmission Spectra of Polyatomic MoleculesNonradiative Relaxation of Polyatomic MoleculesChromophoresSolvent Effects in Electronic SpectroscopySummaryProblemsBibliography Raman and Resonance Raman SpectroscopyIntroductionSelection Rules in Raman ScatteringPolarization in Raman ScatteringRotational and Vibrational Dynamics in Raman ScatteringAnalysis of Raman Excitation ProfilesSurface-Enhanced Raman ScatteringSummaryProblemsBibliography Nonlinear Optical SpectroscopyIntroductionClassical Approaches to Nonlinear Optical ProcessesQuantum Mechanical Approach to Nonlinear Optical ProcessesFeynman Diagrams and Calculation of Time-Dependent Response Functions Experimental Applications of Nonlinear ProcessesSummaryProblemsBibliography Time-Resolved SpectroscopyIntroductionTime-Resolved Fluorescence SpectroscopyTime-Resolved Four Wave Mixing ExperimentsTransient Grating and Photon Echo Experiments Two-Dimensional SpectroscopySummaryProblemsBibliography Appendix A Math ReviewVectors and Tensors in Three DimensionsMatricesOperations with Cartesian and Spherical TensorsSpherical HarmonicsWigner Rotation Functions and Spherical TensorsThe Clebsch-Gordan Series and 3j Symbols Appendix B Principles of ElectrostaticsUnitsSome Applications of Gauss’ LawSome Mathematical Details Appendix C Group TheoryPoint Groups and Symmetry OperationsInformation Conveyed by The Character TablesDirect Products and Reducible Representations Character Tables

Jeanne L. McHale is Professor Emerita at Washington State University, where her research is devoted to the study of molecular aggregates and nanomaterials relevant to solar energy conversion. She is a fellow of the American Association for the Advancement of Science and the author or coauthor of more than 100 publications. In addition to Molecular Spectroscopy, she co-edited the Handbook of Luminescent Semiconductor Materials with Leah Bergman, published by Taylor & Francis in 2011.