Experimental and theoretical study of photo-dissociation spectroscopy of pyrene dimer radical cations stored in a compact electrostatic ion storage ring.

In this paper, we present an experimental and theoretical study of the photo-dissociation of free-flying dimer radical cations of pyrene (C16H10)2+. Experimentally, the dimers were produced in the plasma of an electron cyclotron resonance ion source and stored in an electrostatic ion storage ring, the Mini-Ring for times up to 10 ms and the photo-dissociation spectrum was recorded in the 400 to 2000 nm range. Two broad absorption bands were observed at 550 (2.25 eV) and 1560 nm (0.79 eV), respectively. Theoretical simulations of the absorption spectrum as a function of the temperature were performed using the Density Functional based Tight Binding approach within the Extended Configuration Interaction scheme (DFTB-EXCI) to determine the electronic structure. The simulation involved all excited electronic states correlated asymptotically with the five lowest excited states D1-D5 of the monomer cation and a Monte Carlo exploration of the electronic ground state potential energy surface. The simulations exhibit three major bands at 1.0, 2.1 and 2.8 eV respectively. They allow assigning the experimental band at 1560 nm to absorption by the charge resonance (CR) excited state correlated with the ground state of the monomer D0. The band at 550 nm is tentatively attributed to dimer states correlated with excited states D2-D4, in the monomer cation. Simulations also show that the CR band broadens and shifts towards longer wavelength with increasing temperature. It results from the dependence on the geometry of the energy gap between the ground state and the lowest excited state. The comparison of the experimental spectrum with theoretical spectra at various temperatures allows us to estimate the temperature of the stored (C16H10)2+ in the 300-400 K range, which is also in line with the expected temperatures of the ions deduced from the analysis of the natural decay curve.

Photo-dissociation of naphthalene dimer cations stored in a compact electrostatic ion storage ring.

Naphthalene dimer cations [C10H8]2 + have been produced by using an electron cyclotron resonance plasma ion source and stored in a compact electrostatic ion storage ring. We show that the radiative cooling of these cations is much slower than the isolated monomer naphthalene cations. We also report on photo-dissociation studies in the gas phase of naphthalene dimer cations at high internal energy. The dissociation energy is estimated to 0.5 eV in close agreement with previous measurements but a factor of 2 smaller than recent (density functional theory (DFT) and ab initio) theoretical studies. As uncertainties on theory as well as on the experiment cannot be as large as this difference, we conclude that this discrepancy may be due to temperature effects with possible isomerization. As an interpretation of the photo-dissociation spectrum of naphthalene dimer cations, we propose a tentative simple analytical model based on effective Morse potentials. These effective potentials are expected to "average" temperature effects that would apparently result in a smaller energy difference between the fundamental and dissociation states due to the twisting vibration modes of the naphthalene dimer cations.