Attosecond chronoscopy of photoemission

Recent advances in ultrafast laser spectroscopy have made it possible to study the electron dynamics for physical and chemical processes at the atomic level in real time. This article reviews the concepts and techniques that are necessary to understand and interpret these experiments with the focus on time-resolved photoemission. Recent advances in the generation of well-characterized subfemtosecond laser pulses have opened up unpredicted opportunities for the real-time observation of ultrafast electronic dynamics in matter. Such attosecond chronoscopy allows a novel look at a wide range of fundamental photophysical and photochemical processes in the time domain, including Auger and autoionization processes, as well as photoemission from atoms, molecules, and surfaces, complementing conventional energy-domain spectroscopy. Attosecond chronoscopy raises fundamental conceptual and theoretical questions as to which novel information becomes accessible and which dynamical processes can be controlled and steered. Several of these questions, currently a matter of lively debate, are addressed in this review. The focus is placed on one prototypical case, the chronoscopy of the photoelectric effect by attosecond streaking. Is photoionization instantaneous or is there a finite response time of the electronic wave function to the photoabsorption event? Answers to this question turn out to be far more complex and multifaceted than initially thought. They touch upon fundamental issues of time and time delay as observables in quantum theory. Recent progress of our understanding of time-resolved photoemission from atoms, molecules, and solids is reviewed. Unresolved and open questions are highlighted and future directions are discussed addressing the observation and control of electronic motion in more complex nanoscale structures and in condensed matter.