Cooling of isolated anthracene cations probed with photons of different wavelengths in the Mini-Ring

摘要

We report on a direct measurement of the Internal Energy Distribution (IED) shift rate of an initially hot polycyclic aromatic hydrocarbon (PAH) molecular ensemble, anthracene cations (C14H10+). The ions were produced in an electron cyclotron resonance (ECR) ion source and stored in an electrostatic ion storage ring, the Mini-Ring. Laser pulses of two wavelengths were sent successively to merge the stored ion bunch at different storage times to enhance the neutral fragment yield due to fast laser induced dissociation. Using this technique, we have been able to determine directly the energy shift rate of the IED, without involving any theoretical simulation or any assumption on dissociation rates, cooling rates, or the initial IED. Theoretical energy shift rates have been estimated from the evolution of simulated IEDs by taking into account the effects of the unimolecular dissociation and two radiative decay mechanisms: the Poincare fluorescence and the infrared vibrational emission. The comparison between the experimental results and the model provides new evidence of the important role of the Poincare fluorescence in the overall cooling process of anthracene cations. Although in the short time range the commonly accepted intuition says that the cooling would result mostly from the dissociation of the hottest ions (depletion cooling), we demonstrate that the Poincare fluorescence is the dominant contribution (about 85%) to the net cooling effect. Published by AIP Publishing.