Getting Started on Time-Resolved Molecular Spectroscopy

Description

This textbook provides an overview of the basics of ultrafast molecular spectroscopy starting from time-dependent quantum mechanical perturbation theory in Hilbert space. It emphasizes the dynamics of nuclear and electronic motion, initiated and monitored by femtosecond laser pulses, which underlie the generation of nonlinear optical signals and inform their interpretation. Topics include short-pulse electronic absorption, the molecular adiabatic approximation, transient-absorption spectroscopy, vibrational adiabaticity during conformational change, femtosecond stimulated Raman spectroscopy, multi-dimensional electronic spectroscopy and wave-packet interferometry, and two-dimensional wave-packet interferometry of electronic excitation-transfer systems. The treatment is based on time-dependent quantum mechanics as it is presented in graduate-level quantum mechanics courses. It is designed to be accessible to beginning practitioners of ultrafast spectroscopy and is meant to serve as a bridge to more advanced treatises and research publications. Numerous exercises are embedded in the text to explore and expand upon the physical ideas encountered in this important research field. "This book presents an insightful theoretical formulation of ultrafast molecular spectroscopy. It will be a valuable resource for researchers seeking to understand the connection between quantum mechanics and spectra." -- Nancy Makri, University of Illinois at Urbana-Champaign Jeff Cina earned a BS in Mathematics at UW-Madison, a PhD in Theoretical Physical Chemistry at UC-Berkeley, and carried out post-doctoral research at MIT. After teaching and conducting research at The University of Chicago, he joined the faculty at the University of Oregon in 1995. At Oregon, Cina was a founding member of the Oregon Center for Optics, now the Oregon Center for Optical, Molecular, and Quantum Science. Cover Titlepage Copyright Preface Acknowledgements Contents 1 Short-pulse electronic absorption 1.1 Basic set-up 1.2 Energy changes of molecule and field 1.3 Expectation values 1.4 The Heller formula 1.5 Systems starting in thermal equilibrium 1.6 Example absorption calculations 2 Adiabatic approximation 2.1 Molecular Hamiltonian 2.2 Molecular eigenstates 3 Transient-absorption spectroscopy: Making ultrashort pulses worthwhile 3.1 Model Hamiltonian and signal expression 3.2 Transient-absorption dipole 3.3 Exemplary calculations 4 How fissors works: Femtosecond stimulated Raman spectroscopy as a probe of conformational change 4.1 Basic idea 4.2 Signal formation 4.3 Fissors dipole 4.4 Example signal calculation 5 Transient-absorption reprise: Taking advantage of vibrational adiabaticity 5.1 Transient-absorption signal under vibrational adiabaticity 5.2 Calculated transient-absorption signals 6 Two and a half approaches to two-dimensional wave-packet interferometry 6.1 Introduction 6.2 Measured quantities 6.3 Quantum mechanical aspects 6.4 Example signals 7 Two-dimensional wave-packet interferometry for an electronic energy-transfer dimer 7.1 Energy-transfer dimer 7.2 Whoopee signal 7.3 Illustrative calculations Appendix A Electromagnetic energy change due to light absorption Appendix B Delay regions for doubly excited-state-visiting overlaps in the difference-phased singly excited-state populations Appendix C Delay regions for overlaps contributing to the difference-phased doubly excited-state population Index