Polariton Chemistry

Joel Yuen-Zhou, PhD is Associate Professor in the Department of Chemistry and Biochemistry at the University of California, San Diego. His research focuses on the theoretical description of novel interactions between light and molecular matter in the weak, strong, and ultrastrong coupling regimes. His pioneering work on polariton chemistry has been recognized with several awards including a Sloan Fellowship as well as the NSF CAREER, DOE Early Career and Camille-Dreyfus Teacher Scholar awards. Noel C. Giebink, PhD, is a Professor in the Department of Electrical Engineering and Computer Science at the University of Michigan. His research focuses on light-matter interaction and the physics of organic semiconductor materials and devices. He is a senior member of IEEE, Optica, and SPIE, and has been recognized with the DARPA YFA, AFOSR YIP, and NSF CAREER awards. Raphael F. Ribeiro, PhD is Assistant Professor in the Department of Chemistry at Emory University, Atlanta since 2020. His research is focused on theoretical models and simulation of equilibrium and non-equilibrium chemical dynamics in mesoscopic materials. His work has been recognized with awards that include NSF CAREER award and a Young Investigator Award by the Physical Chemistry Division of the American Chemical Society.

• Preface xiAcknowledgments xviiPart I Basic Concepts 11 Ultrafast Dynamics Under Electronic Strong Light–Matter Coupling 3Courtney DelPo and Gregory Scholes1.1 Introduction: Energy Levels – Central to Science 31.2 Electronic Strong Coupling in Transient Absorption and Reflection Spectroscopy 71.2.1 Description of Transient Absorption and Reflection Spectroscopy 71.2.2 Polariton Signatures in Transient Absorption and Reflection Spectroscopy 71.3 Electronic Strong Coupling in Broadband and Two-dimensional Electronic Spectroscopy 101.4 Electronic Strong Coupling in Applications 111.5 Future Outlook of Ultrafast Dynamics in Electronic Strong Coupling 13References 132 Molecular Strong Coupling: The Quantum to Classical Transition 17William L. Barnes2.1 Introduction 172.2 Interaction Strength and the Bulk Material Response 192.3 Comparing Quantum and Classical 24Acknowledgments 25References 263 The Role of Cavity in Polaritonics: Plasmonic Nanoparticles, Self-hybridized Polaritons, and Casimir Self-assembly 29Oleg V. Kotov and Timur O. Shegai3.1 Plasmonic Resonators 303.1.1 Light–Matter Interactions Using Plasmonic Resonators and Their Arrays 303.1.2 Single Plasmonic Resonators 333.1.3 The Single-emitter Limit 343.1.4 Plexcitonic Photophysics and Photochemistry 373.2 Self-hybridized Polaritons 413.3 Casimir Microcavities 443.4 Conclusions and Outlook 46References 474 Plexciton Photophysics 61Daniel Finkelstein-Shapiro4.1 Goal of this Chapter 614.2 What is a Plexciton and How Is It Different from a Cavity Polariton 614.3 Synthesis of Plexcitons and Their Structure: Influence and Consequence on the Photophysics 644.3.1 Colloidal Systems-based on Organic Molecules 644.3.2 Open Cavities 654.3.3 Surface Nanocavities 654.4 Photophysics of Plexcitons 654.4.1 Emitters 664.4.2 Metallic Nanoparticle 674.4.3 Plexcitons 694.5 Spectral Signatures 734.5.1 Suggestions for Approaching Transient Absorption Spectra of Plexcitons 754.6 Applications 754.6.1 Photostability 754.6.2 Hot Electron Hole Generation 754.6.3 Chiral Cavities and Phase Transitions 764.7 Conclusion 76Acknowledgments 76References 765 Coupling of Nanocavities to Molecules 83Rohit Chikkaraddy and Jeremy Baumberg5.1 Light and Molecules 835.2 Optical Cavities 855.3 Free-electron Model 875.4 Introduction to Plasmons 885.4.1 Propagating Surface Plasmon Polaritons 905.4.2 Localized Surface Plasmon Polaritons 905.5 Cavity Description for Plasmon Modes 915.5.1 Qualify Factor 925.5.2 Mode Volume 925.6 Nanocavities 935.6.1 Nanoparticle on Mirror 935.6.2 Sensing Molecules in the Gap 965.6.3 Effect of Nanoparticle Size and Shape 965.7 Light–Matter Coupling 975.7.1 Weak-coupling Regime and Purcell Effect 995.7.2 Strong Coupling 1035.7.3 Single-molecule Strong Coupling 1075.8 Conclusion 109References 109Part II Spectroscopy and Dynamics 1156 Nonlinear Spectroscopy Under Vibrational Strong Coupling 117Adam D. Dunkelberger, Cynthia G. Pyles and Jeffrey C. Owrutsky6.1 Introduction 1176.2 Experimental Considerations 1206.3 Understanding the Nonlinear Response of MVP 1216.4 Early Delays 1216.5 Later Delays 1226.6 Intermediate Delays 1276.7 Optical and Photophysical Opportunities 1286.8 Concluding Remarks 130Acknowledgments 131References 1317 Quantum Dynamics, Optical Signals, and Spectroscopy of Molecular Polaritons 139Zhedong Zhang7.1 Introduction 1397.2 Quantum Electrodynamics of Molecular Polaritons 1407.3 Pump-probe Spectra for Molecular Polaritons 1437.4 Multidimensional Infrared Spectroscopy for Vibrational Polaritons: Density-matrix Theory 1447.4.1 Gateway-window Formalism 1447.4.2 Cooperativity Versus Localization 1477.4.3 Stochastic Model for Vibrational Polaritons 1487.4.4 Simulations of 2DIR Spectra for VPs 1507.5 Multidimensional Electronic Spectroscopy for Exciton Polaritons: Heisenberg–Langevin Theory 1547.5.1 Langevin Model for Exciton Polaritons 1547.5.2 Correlation Functions of Vibrations 1577.5.3 Absorption Spectrum 1587.5.4 Time-resolved Emission of Polaritons 1597.5.5 Two-dimensional Polariton Spectroscopy 1597.5.6 Connection to Polariton Pump-probe Spectra 162Acknowledgments 163References 1648 Molecular Dynamics Simulations of Exciton–Polaritons in Organic Microcavities 167Gerrit Groenhof, Ruth H. Tichauer and Ilia Sokolovskii8.1 Introduction 1678.2 Molecular Dynamics in the Collective Strong Coupling Regime 1688.2.1 Born–Oppenheimer Approximation in the Electronic Strong Coupling Regime 1698.2.2 Quantum Mechanics/Molecular Mechanics 1698.2.3 Multiscale Tavis–Cummings Hamiltonian 1708.2.4 Multimode Fabry–Pérot Cavities 1728.2.5 Semiclassical Molecular Dynamics 1748.3 Applications 1778.3.1 Polariton Relaxation 1778.3.2 Polariton Transport 1798.3.3 Polaritonic Photochemistry 1828.4 Summary and Outlook 185References 1859 Disorder in Cavity-modified Transport and Chemistry 193David Hagenmüller, Jérôme Dubail, Francesco Mattiotti, Guido Pupillo and Johannes Schachenmayer9.1 Introduction 1939.2 Semilocalization 1949.2.1 The Disordered TC Model with Hopping 1959.2.2 Arrowhead Matrix Model and Dark State Multifractality 1999.3 The Influence of Disorder and Semilocalization on Vibrational Dynamics 2039.3.1 The Holstein–Tavis–Cummings Model 2039.3.2 Vibrational Entanglement and Numerical Simulations 2059.3.3 Dynamics After Photo-excitation 2079.4 Conclusion and Outlook 211References 213Part III Applications 21910 Engineering Organic Exciton–Polariton Condensates in Microcavities 221Sitakanta Satapathy and Vinod M. Menon10.1 Introduction 22110.2 Mechanism of Polariton Condensation in Organic Microcavities 22310.2.1 Radiative Pumping 22410.2.2 Vibron-assisted Relaxation 22510.3 Experimental Signatures of Polariton Condensation in Organic Microcavities 22510.4 The Molecular Medley for Polariton Condensation 22710.4.1 Single Crystalline Systems 22710.4.2 Low Molecular Weight Emitters 23010.4.3 Polymers 23510.4.4 Host–Guest Systems 23810.5 Summary 242References 24311 Kinetic Models for Polariton Relaxation in Organic Microcavities and Comparison to Experiments 247Tomohiro Ishii, Stéphane Kéna-Cohen, Felipe Herrera and Chihaya Adachi11.1 Introduction 24711.2 Modeling Polariton Kinetics in the Linear and Nonlinear Regime 24911.2.1 Polariton Kinetics in the Linear Regime 24911.2.2 Polariton Kinetics in the Nonlinear Regime 25411.3 Polariton Relaxation Mechanisms 25711.3.1 Radiative Pumping Process (1): Initial Experiments 25711.3.2 Radiative Relaxation 26011.3.3 Nonradiative Relaxation 26211.4 Comparison Between the Experimentally and Theoretically Estimated W ep in BSBCz-EH System 26411.5 Conclusion 265References 26512 Reactions and Assembly Under Vibrational Strong Coupling 271Kenji Hirai and Hirohi Uji-i12.1 Introduction 27112.2 Vibrational Strong Coupling 27212.3 Chemical Reactions Under VSC 27512.3.1 Organic Reactions 27612.3.2 Enzymatic Reactions Under VSC 28012.3.3 Symmetry of Molecular Vibrations 28112.3.4 Interpretation of Vibrational Strong Coupling 28112.3.5 Self-assembly and Crystallization Under VSC 28212.4 Summary 283References 28313 Controlling and Probing Molecular Polaritons 289Michael A. Michon and Blake S. Simpkins13.1 Introduction 28913.2 Analytical Description of Cavities 28913.2.1 Treatment of Lossless Mirrors Bounding an Absorbing Medium 28913.2.2 Semiclassical Coupled Oscillators 29313.3 Nonidealities: That We Must, Nevertheless, Deal with 29413.3.1 Details for Dealing with Cavities 29413.3.2 Spatially Dependent Response 29613.3.3 Line Broadening 29813.4 Current Challenges and Proposed Best Practices 29913.4.1 Current Challenges 30013.4.2 Measuring Reaction Rates in Optical Cavities 30113.4.3 Validating Angle-independent Rate Extraction 30313.4.4 Proposed Cavity System Design 30713.5 Conclusion 311References 311Part IV Frontiers 31514 A Comparison of Coulomb and Multipolar Gauge Theories of Cavity Quantum Electrodynamics 317Adam Stokes and Ahsan Nazir14.1 Introduction 31714.2 Perfect Cavity 31814.2.1 Empty Fabry–Pérot Cavity 31814.2.2 Perfect Cavity Containing Matter 31914.3 Gauge Relativity 32414.3.1 Relativity and Invariance 32414.3.2 Gauge Nonrelativistic Predictions 32514.3.3 A Case Study in Gauge Relativity and Gauge Ambiguities: Dipolar Photon Emission and Detection 32914.4 Imperfect Cavities 34714.4.1 Phenomenological Descriptions 34714.4.2 Subsystem Gauge Relativity in Macroscopic QED 35214.5 Conclusions 356References 357Appendix A: Computation of K and G, and the Field Canonical Commutation Relation in the Case of a Perfect Parallel Plate Cavity 362Appendix B: Born–Markov-secular Master Equation for the Dipole in a Fabry–Pérot Cavity 364Appendix C: Emission Rates of a Dipole Near a Single Plate 367Appendix D: Proof that the Sum of Imperfect Cavity Lorenztians Gives a Dirac Comb in the Perfect Cavity Limit 36815 The Vacuum in Ultrastrong Coupling Cavity Quantum Electrodynamics 369Peter Rabl15.1 Introduction 36915.2 The Dicke Model 37015.2.1 Collective Light–Matter Interactions 37015.2.2 Superradiant Instability 37115.3 Effective Models in Cavity QED 37215.3.1 Cavity QED in the Coulomb Gauge 37215.3.2 Cavity QED in the Dipole Gauge 37415.4 The Ground States in Cavity QED 37715.4.1 Boundary-induced Ferroelectricity 37715.4.2 Collective Ultrastrong Coupling Regime 37815.4.3 Nonperturbative Coupling Regime 37915.4.4 Ground-state Phases in Cavity QED 38115.5 Conclusions 382References 382Afterword 385Index 387