Since the first demonstration of the generation of attosecond pulses (1 as = 10⁻¹⁸ s) in the extreme-ultraviolet spectral region, several measurement techniques have been introduced, at the beginning for the temporal characterization of the pulses, and immediately after for the investigation of electronic and nuclear ultrafast dynamics in atoms, molecules and solids with unprecedented temporal resolution. The attosecond spectroscopic tools established in the last two decades, together with the development of sophisticated theoretical methods for the interpretation of the experimental outcomes, allowed to unravel and investigate physical processes never observed before, such as the delay in photoemission from atoms and solids, the motion of electrons in molecules after prompt ionization which precede any notable nuclear motion, the temporal evolution of the tunneling process in dielectrics, and many others. This review focused on applications of attosecond techniques to the investigation of ultrafast processes in atoms, molecules and solids. Thanks to the introduction and ongoing developments of new spectroscopic techniques, the attosecond science is rapidly moving towards the investigation, understanding and control of coupled electron–nuclear dynamics in increasingly complex systems, with ever more accurate and complete investigation techniques. Here we will review the most common techniques presenting the latest results in atoms, molecules and solids.

The electro-optical properties of most semiconductors and insulators of technological interest are dominated by the presence of electron-hole quasi-particles, called excitons. The manipulation of excitons in dielectrics has recently received great attention, with possible applications in different fields including optoelectronics and photonics. Here, we apply attosecond transient reflection spectroscopy in a sequential two-foci geometry and observe sub-femtosecond dynamics of a core-level exciton in bulk MgF₂ single crystals. Furthermore, we access absolute phase delays, which allow for an unambiguous comparison with theoretical calculations. Our results show that excitons surprisingly exhibit a dual atomic- and solid-like character, which manifests itself on different time scales. While the former is responsible for a femtosecond optical Stark effect, the latter dominates the attosecond excitonic response. Further theoretical investigation reveals a link with the exciton sub-femtosecond nanometric motion and allows us to envision a new route to control exciton dynamics in the close-to-petahertz regime.

DNA owes its remarkable photostability to its building blocks—the nucleosides—that efficiently dissipate the energy acquired upon ultraviolet light absorption. The mechanism occurring on a sub-picosecond time scale has been a matter of intense debate. Here we combine sub-30-fs transient absorption spectroscopy experiments with broad spectral coverage and state-of-the-art mixed quantum-classical dynamics with spectral signal simulations to resolve the early steps of the deactivation mechanisms of uridine (Urd) and 5-methyluridine (5mUrd) in aqueous solution. We track the wave packet motion from the Franck-Condon region to the conical intersections (CIs) with the ground state and observe spectral signatures of excited-state vibrational modes. 5mUrd exhibits an order of magnitude longer lifetime with respect to Urd due to the solvent reorganization needed to facilitate bulky methyl group motions leading to the CI. This activates potentially lesion-inducing dynamics such as ring opening. Involvement of the ¹nπ* state is found to be negligible.