RESUMO
Radiation-induced damage of biological matter is an ubiquitous problem in nature. The influence of the hydration environment is widely discussed, but its exact role remains elusive. Utilising well defined solvated-molecule aggregates, we experimentally observed a hydrogen-bonded water molecule acting as a radiation protection agent for ionised pyrrole, a prototypical aromatic biomolecule. Pure samples of pyrrole and pyrrole(H2O) were outer-valence ionised and the subsequent damage and relaxation processes were studied. Bare pyrrole ions fragmented through the breaking of C-C or N-C covalent bonds. However, for pyrrole(H2O)+, we observed a strong protection of the pyrrole ring through the dissociative release of neutral water or by transferring an electron or proton across the hydrogen bond. Overall, a single water molecule strongly reduces the fragmentation probability and thus the persistent radiation damage of singly-ionised pyrrole.
RESUMO
Alkali trimers, Ak3, located on the surface of He nanodroplets are triply ionized following multiphoton absorption from an intense femtosecond laser pulse, leading to fragmentation into three correlated Ak+ ions. Combining the information from threefold covariance analysis of the emission direction of the fragment ions and their kinetic energy distributions P(Ekin), we find that Na3, K3, and Rb3 have an equilateral triangular structure, corresponding to that of the lowest lying quartet state A2'4, and determine the equilibrium bond distance Req(Na3) = 4.65 ± 0.15 Å, Req(K3) = 5.03 ± 0.18 Å, and Req(Rb3) = 5.45 ± 0.22 Å. For K3 and Rb3, these values agree well with existing theoretical calculations, while for Na3, the value is 0.2-0.3 Å larger than the existing theoretical results. The discrepancy is ascribed to a minor internuclear motion of Na3 during the ionization process. In addition, we determine the distribution of internuclear distances P(R) under the assumption of fixed bond angles. The results are compared to the square of the internuclear wave function |Ψ(R)|2.