2021, Zalibera, Michal, Ziegs, Frank, Schiemenz, Sandra, Dubrovin, Vasilii, Lubitz, Wolfgang, Savitsky, Anton, Deng, Shihu H.M., Wang, Xue-Bin, Advoshenko, Stanislav M., Popov, Alexey A.

We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of YxSc3−xN@C80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1–T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

2008, Ansari, Z., Böttcher, M., Manschwetus, B., Rottke, H., Sandner, W., Verhoef, A., Lezius, M., Paulus, G.G., Saenz, A., Milošević, D.B.

Strong-field photoionization of argon dimers by a few-cycle laser pulse is investigated using electron-ion coincidence momentum spectroscopy. The momentum distribution of the photoelectrons exhibits interference due to the emission from the two atomic argon centres, in analogy with a Young's doubleslit experiment. However, a simulation of the dimer photoelectron momentum spectrum based on the atomic spectrum supplemented with a theoretically derived interference term leads to distinct deviations from the experimental result. The deviations may have their origin in a complex electron dynamics during strong-field ionization of the Ar2 dimer. © IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.

2016, Odžak, S., Hasović, E., Becker, W., Milošević, D.B.

We investigate laser-assisted electron-ion recombination (LAR), high-order harmonic generation (HHG) and above-threshold ionization (ATI) of argon atoms by a bicircular laser field, which consists of two coplanar counter-rotating circularly polarized fields of frequencies rω and sω. The energy of soft x rays generated in the LAR process is analyzed as a function of the incident electron angle and numerical results of direct recombination of electrons with Ar+ ions are presented. We also present the results of HHG by a bicircular field and confirm the selection rules derived earlier for inert-gas atoms in a p ground state. We show that the photoelectron spectra in the ATI process, presented in the momentum plane, as well as the LAR spectra exhibit the same discrete rotational symmetry as the applied field.