1. Introduction 2. Quantum Dynamics in Hilbert Space 3. The Density Operator and Quantum Dynamics in Liouville Space 4. Quantum Electrodynamics, Optical Polarization, and Nonlinear Spectroscopy 5. Nonlinear Response Functions and Optical Susceptibilities 6. The Optical Response Functions of a Multilevel System with Relaxation 7. Semiclassical Simulation of the Optical Response Functions 8. The Cumulant Expansion and the Multimode Brownian Oscillator Model 9. Fluorescence, Spontaneous-Raman and Coherent-Raman Spectroscopy 10. Selective Elimination of Inhomogeneous Broadening Photon Echoes 11. Resonant Gratings, Pump-Probe, and Hole Burning Spectroscopy 12. Wavepacket Dynamics in Liouville Space The Wigner Representation 13. Wavepacket Analysis of Nonimpulsive Measurements 14. Off-Resonance Raman Scattering 15. Polarization Spectroscopy Birefringence and Dichroism 16. Nonlinear Response of Molecular Assemblies The Local-Field Approximation 17. Many Body and Cooperative Effects in the Nonlinear Response
Introduction 2. Quantum Dynamics in Hilbert Space 3. The Density Operator and Quantum Dynamics in Liouville Space 4. Quantum Electrodynamics, Optical Polarization, and Nonlinear Spectroscopy 5. Nonlinear Response Functions and Optical Susceptibilities 6. The Optical Response Functions of a Multilevel System with Relaxation 7. Semiclassical Simulation of the Optical Response Functions 8. The Cumulant Expansion and the Multimode Brownian Oscillator Model 9. Fluorescence, Spontaneous-Raman and Coherent-Raman Spectroscopy 10. Selective Elimination of Inhomogeneous Broadening Photon Echoes 11. Resonant Gratings, Pump-Probe, and Hole Burning Spectroscopy 12. Wavepacket Dynamics in Liouville Space The Wigner Representation 13. Wavepacket Analysis of Nonimpulsive Measurements 14. Off-Resonance Raman Scattering 15. Polarization Spectroscopy Birefringence and Dichroism 16. Nonlinear Response of Molecular Assemblies The Local-Field Approximation 17. Many Body and Cooperative Effects in the Nonlinear Response
Abstract This chapter focuses on spectroscopic applications of time dependent quantum mechanics focusing on molecular spectroscopy in condensed phases. (1) Molecular spectroscopy in the dressed state picture. (2) Resonance Raman scattering. (3) Resonance energy transfer. (4) Collective excitation and emission. (5) Thermal relaxation and dephasing (the Bloch equations, relaxation of a prepared state, dephasing (decoherence), the absorption lineshape, homogeneous and inhomogeneous broadening, motional narrowing, thermal effects in resonance Raman scattering). (6) A case study: Resonance Raman scattering and fluorescence from Azulene in a Naphthalene matrix. (7) Probing inhomogeneous bands (hole-burning spectroscopy, photon echoes, single-molecule spectroscopy. (8) Optical response functions.
Spectroscopy, the study of matter via its interactions with light, is a vast subject that includes many of humanity's principle means of probing the fundamental structure of matter. Though usually understood from the perspective of classical light, important effects arise due to the quantum nature of the electromagnetic field. Additionally, the quantum vacuum can serve as an effective couple between molecules in the system, generating many-body interactions and cooperative processes in the material. While many techniques are well-described classically, quantum-field corrections can dominate the desired signals in certain cases, such as cascading in higher-order n-wave mixing signals, and are key for experimental interpretation. Even spontaneous emission and light scattering are best understood from the perspective of quantum fields. In this thesis, we utilize a systematic procedure, based on the density matrix in Liouville space, to give a rigorous description of elementary quantum-field effects in nonlinear spectroscopy, with specific examples made to ultrafast x-ray and optical techniques.
Optical spectroscopy provides a useful tool for probing the structure and dynamics of solids. Over the years, optical methods have evolved from absorption spectroscopy to more complex methods such as spectral hole burning, photon echoes, and luminescence line narrowing. The absorption spectrum provides information about inhomogeneous broadening, while the latter approaches provide information about the systematics of the homogeneous line shape information that is often obscured by inhomogeneous broadening. When external perturbations such as strain or electric fields are applied, details of the local site can be obtained. Recently, the ultimate limit of optical spectroscopy has been attained, in which the spectral properties of individual single impurity molecules in a solid can be measured, with all ensemble averaging removed. This novel regime has provided additional, previously unobtainable, information on a highly local scale, such as the direct observation of the spectral shifting of a single molecule produced by configurational transitions of the host. It is to be expected that further surprises await us in this new frontier of single-molecule spectroscopy in solids.
W1 Resonant Pulse Propagation I.- W1-1 Some Nonlinear Properties of Pulse Propagation.- W1-2 Self-Induced Transparency in the Broadline and Narrowline Limits and Applications.- W1-3 Observation of Zero-Degree Pulse Propagation in a Resonant Medium.- W1-4 Higher Conservation Laws and Coherent Pulse Propagation.- W2 Quantum Electrodynamics and Alternative Theories I.- W2-1 Survey of the Present Status of Neoclassical Radiation Theory.- W2-2 A Test of Jaynes' Neoclassical Theory: Incoherent Resonance Fluorescence from a Coherently Excited State.- W2-3 Experimental Limitations to the Validity of Semiclassical Radiation Theories.- W2-4 Time Delay Statistics of Photoelectric Emissions: An Experimental Test of Classical Radiation Theory.- W3 Coherence Effects in Spontaneous Emission I.- W3-1 Non-Linear Radiation Reaction.- W3-2 Master Equations in the Theory of Incoherent and Coherent Spontaneous Emission.- W3-3 Influence of Resonant Frequency Shifts on Superradiant Damping.- W3-4 Spontaneous Emission Rate in the Presence of a Mirror.- W4 Coherence I.- W4-1 Atomic Coherent States in Quantum Optics.- W4-2 Coherent States in Modern Physics.- W4-3 Debye Representation and Multipole Expansion of the Quantized Free Electromagnetic Field.- W4-4 Volume of Coherence.- T1 Quantum Electrodynamics and Alternative Theories II.- T1-1 A Quantum Treatment of Spontaneous Emission without Photons.- T1-2 Finite Quantum and Classical Electrodynamics.- T1-3 The Use of Classical Solutions in Quantum Optics.- T1-4 Raman Effect in Semiclassical Theory.- T2 Light Scattering I.- T2-1 Theory of Resonant Light Scattering Processes in Solids.- T2-2 A Generalized Extinction Theorem and Its Role in Scattering Theory.- T2-3 Mode Analysis and Mode Coupling of Electromagnetic Fields in Spatially Dispersive Media.- T2-4 Amplitude Stabilization of Pulses from a Q-Switched Ruby Laser by Means of Interaction with a Non-Linear Medium.- T3 Correlation and Fluctuation Measurements.- T3-1 Two-Photon Time Distributions in Mixed Light Beams.- T3-2 Photocounting Inversion in Presence of Dead Time Effects.- T3-3 Image Reconstruction from the Modulus of the Correlation Function: A Practical Approach to the Phase Problem of Coherence Theory.- T3-4 Photon-Correlation Spectroscopy.- T3-5 Multi-Time Intervals Distributions of Photoelectrons from Stationary Pseudo-Thermal Light with Gaussian Spectrum.- T4 Light Scattering II.- T4-1 Adventures in Green's Land: Light Scattering in Anisotropic Media.- T4-2 Intensity Fluctuation Techniques in Light Scattering.- T4-3 Coherence Properties of Light through a Liquid Crystal.- T4-4 C. Non-Critical Rayleigh Scattering from Pure Liquids.- T5 Coherence Effects in Spontaneous Emission II.- T5-1 Cooperative Effects in Spontaneous Emission.- T5-2 Amplified Spontaneous Emission.- T5-3 Non-Gaussian Statistics of Superradiant Radiation from Saturated Xenon 3.5?m Laser Amplifier.- T5-4 On the Theory of Radiating Electrons.- T6 Coherent Light Interactions.- T6-1 Atomic and Molecular Spectroscopy by Saturation with Coherent Light.- T6-2 Response Functions for Strongly Driven Systems.- T6-3 Mechanism of Interaction of Picosecond Light Pulses with Matter Yielding Self-Trapping.- T6-4 Resonance Fluorescence Lineshapes with Intense Applied Fields.- T6-5 Electron Beams as Carriers of Optical Coherence.- T7 Lasers.- T7-1 Detuned Single Mode Laser and Detailed Balance.- T7-2 Tunable Raman Lasers.- T7-3 Dye Lasers: Recent Advances in Tunable Systems.- F1 Quantum Electrodynamics and Alternative Theories III.- F1-1 A Theory of Light without Photons: Implications from Fermis to Light Years.- F1-2 Blackbody Heat Capacity and Action-at-a-Distance Electrodynamics.- F1-3 The Implications of Radiative Equilibrium in Jaynes' Extension of Semiclassical Radiation Theory.- F1-4 A Quantum Electrodynamic Investigation of the Jaynes-Crisp-Stroud Approach to Spontaneous Emission.- F1-5 Critical Comments on Radiation Theory.- F2 Resonant Pulse Propagation II.- F2-1 Cooperative Phenomena in Resonant Propagation.- F2-2 Theory of Sub-Cooperation-Limit Optical Pulses in Resonant Absorbers.- F2-3 Multiple Pulse Chirping in Self-Induced Transparency.- F2-4 Coupled Superradiance Master Equations: Application to Fluctuations in Coherent Pulse Propagation in Resonant Media.- F3 Coherence II.- F3-1 The Laser-Phase Transition Analogy - Recent Developments.- F3-2 Multiple-Time-Scale Analysis of Coherent Radiation.- F3-3 Orthogonal Operators and Phase Space Distributions in Quantum Optics.- F4 Coherence Effects in Spontaneous Emission III.- F4-1 Radiation by Many Excited Atoms between Mirrors.- F4-2 Transient Coherent Emission.- F4-3 Superradiance from a System of 3-Level Particles.- F4-4 A Quantum Electrodynamic View of Superradiance as a Competition between Stimulated and Spontaneous Atomic Decay.- F5 Post Deadline Session.- F5-1 Third- and Higher-Order Intensity Correlations in Laser Light.- F5-2 Correlation Function of a Laser Beam near Threshold.- F5-3 Localization of Photons.- F5-4 Adiabatic Following and the Self-Defocusing of Light in Rubidium Vapor.- F5-5 Experimental Evidence of an X-Ray Laser.- F5-6 Quantum Theory of Photodetection and Coherence Properties of Electrons.- F5-7 Statistics of Light Scattered by Non-Gaussian Fluctuations.- F6 Quantum Noise.- F6-1 Unified Thermodynamics of Dissipative Structures and Coherence in Nonlinear Optics.- F6-2 The Approach to Thermal Equilibrium in Systems of Coupled Quantum Oscillators Initially in a Generalized Gaussian State.- F6-3 Comparison between Incoherent and Chaotic Sources: Contribution to the Study of the Origin of Bunching Effect.- F6-4 Self-Pulsing in Laser Amplification of Broadband Noise.- Author Index.
Partial table of contents: PART I: GENERAL CONCEPTS AND METHODS OF NONLINEAR OPTICS. Electromagnetic Fields. Classical Description. The Quantized Free Radiation Field. Interaction Between Radiation and Matter. Semiclassical Description of Nonlinear Optics. Statistical and Coherence Properties of the Radiation Field and Their Measurement. Nonstationary Processes. PART II: EFFECTS AND PROCESSES OF NONLINEAR OPTICS. Nonlinear One--photon Processes in Lasers. Nonlinearities in Transient One--photon Processes. Nonlinearities and Qunatum Phenomena in Transient One--photon Processes. Multiphoton Absorption and Emission. Generation of Harmonics and Sum and Difference Frequencies. Parametric Amplification and Oscillation. Stimulated Raman Scattering. Optical Bistability. APPENDIX A: Compilation of Quantum--Theoretical Definitions and Relations. General References. Index.
A theory of optical echo spectroscopies of large polyatomic molecules in condensed phases is developed. Using phase space correlation functions, we examine the interrelationships among the following optical measurements: ordinary photon echo, stimulated photon echo, accumulated photon echo, incoherent accumulated photon echo, and pump–probe absorption. Conditions for the elimination of inhomogeneous broadening in these experiments are specified. A multimode Brownian oscillator model is used to account for high frequency molecular vibrations, as well as solvent modes, and electronic dephasing processes. The effects of quantum beats, spectral diffusion, and homogeneous dephasing on the echo signals are studied and compared in detail with pump–probe and hole burning spectroscopy.