Making molecules in cavity.

Free molecules undergo processes with photons; in particular, they can undergo photoionization and photodissociation, which are relevant processes in nature and laboratory. Recently, it has been shown that in a cavity, the reverse process of photoionization, namely, electron capture becomes highly probable. The underlying mechanism is the formation of a hybrid resonance state. In this work, we demonstrate that the idea of enhanced reverse processes is more general. We discuss the case of the reverse process of photodissociation, namely, making a molecule out of separate atoms in a cavity. For bound electronic states, the interaction of atoms and molecules with quantum light as realized in cavities is known to give rise to the formation of hybrid light-matter states (usually called polaritons). In the scenarios discussed here, the hybrid light-matter states are resonance (metastable) states, which decay into the continuum of either electrons or of the fragments of a molecule. Resonances can substantially enhance the outcome of processes. In addition to the new resonant mechanism of molecule formation, the impact of the hybrid resonances on the scattering cross section of the atoms can be dramatic.

Observation of Nuclear Wave-Packet Interference in Ultrafast Interatomic Energy Transfer.

We report the experimental observation of quantum interference in the nuclear wave-packet dynamics driving ultrafast excitation-energy transfer in argon dimers below the threshold of interatomic Coulombic decay (ICD). Using time-resolved photoion-photoion coincidence spectroscopy and quantum dynamics simulations, we reveal that the electronic relaxation dynamics of the inner-valence 3s hole on one atom leading to a 4s or 4p excitation on the other one is influenced by nuclear quantum dynamics in the initial state, giving rise to a deep, periodic modulation on the kinetic-energy-release (KER) spectra of the coincident Ar^{+}-Ar^{+} ion pairs. Moreover, the time-resolved KER spectra show characteristic fingerprints of quantum interference effects during the energy-transfer process. Our findings pave the way to elucidating quantum-interference effects in ultrafast charge- and energy-transfer dynamics in more complex systems, such as molecular clusters and solvated molecules.

Activating cavity by electrons.

The interaction of atoms and molecules with quantum light as realized in cavities has become a highly topical and fast growing research field. This interaction leads to hybrid light-matter states giving rise to new phenomena and opening up pathways to control and manipulate properties of the matter. Here, we substantially extend the scope of the interaction by allowing free electrons to enter the cavity and merge and unify the two active fields of electron scattering and quantum-light-matter interaction. In the presence of matter, hybrid metastable states are formed at electron energies of choice. The properties of these states depend strongly on the frequency and on the light-matter coupling of the cavity. The incoming electrons can be captured by the matter inside the cavity solely due to the presence of the cavity. The findings are substantiated by an explicit example and general consequences are discussed.