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Light is a preeminent spectroscopic tool for investigating the electronic structure of surfaces. Time-resolved photoelectron spectroscopy has mainly been developed in the last 30 years. It is therefore not surprising that the topic was hardly mentioned in the issue on ‘‘The first thirty years’’ of surface science. In the second thirty years, however, we have seen tremendous progress in the development of time-resolved photoelectron spectroscopy on surfaces. Femtosecond light pulses and advanced photoelectron detection schemes are increasingly being used to study the electronic structure and dynamics of occupied and unoccupied electronic states and dynamic processes such as the energy and momentum relaxation of electrons, charge transfer at interfaces and collective processes such as plasmonic excitation and optical field screening. Using spin- and time-resolved photoelectron spectroscopy, we were able to study ultrafast spin dynamics, electron–magnon scattering and spin structures in magnetic and topological materials. Light also provides photon energy as well as electric and magnetic fields that can influence molecular surface processes to steer surface photochemistry and hot-electron-driven catalysis. In addition, we can consider light as a chemical reagent that can alter the properties of matter by creating non-equilibrium states and ultrafast phase transitions in correlated materials through the coupling of electrons, phonons and spins. Electric fields have also been used to temporarily change the electronic structure. This opened up new methods and areas such as high harmonic generation, light wave electronics and attosecond physics. This overview certainly cannot cover all these interesting topics. But also as a testimony to the cohesion and constructive exchange in our ultrafast community, a number of colleagues have come together to share their expertise and views on the very vital field of dynamics at surfaces. 

Coupling between exciton states across the Brillouin zone in monolayer transition metal dichalcogenides can lead to ultrafast valley depolarization. Using time- and angle-resolved photoemission, we present momentum- and energy-resolved measurements of exciton coupling in monolayer WS2. By comparing full 4D (kx,ky,E,t) data sets after both linearly and circularly polarized excitation, we are able to disentangle intervalley and intravalley exciton coupling dynamics. Recording in the exciton binding energy basis instead of excitation energy, we observe strong mixing between the B1s exciton and An>1 states. The photoelectron energy and momentum distributions observed from excitons populated via intervalley coupling (e.g. K− → K+) indicate that the dominant valley depolarization mechanism conserves the exciton binding energy and center-of-mass momentum, consistent with intervalley Coulomb exchange. On longer timescales, exciton relaxation is accompanied by contraction of the momentum space distribution.