Optical absorption and shape transition in neutral Sn-N clusters with N <= 40: a photodissociation spectroscopy and electric beam deflection study

Neutral Sn-N clusters with N = 6-20, 25, 30, 40 are investigated in a joint experimental and quantum chemical study with the aim to reveal their optical absorption in conjunction with their structural evolution. Electric beam deflection and photodissociation spectroscopy are applied as molecular beam techniques at nozzle temperatures of 16 K, 32 K and 300 K. The dielectric response is probed following the approach in S. Schafer et al., J. Phys. Chem A, 2008, 112, 12312-12319. It is improved on those findings and the cluster size range is extended in order to cover the prolate growth regime. The impact of the electric dipole moment, rotational temperature and vibrational excitation on the deflection profiles is discussed thoroughly. Photodissociation spectra of tin clusters are recorded for the first time, show similarities to spectra of silicon clusters and are demonstrated to be significantly complicated by the presence of multiphoton absorption in the low-energy region and large excess energies upon dissociation which is modelled by the RRKM theory. In both experiments two isomers for the clusters with N = 8, 11, 12, 19 need to be considered to explain the experimental results. Triple-capped trigonal prisms and double-capped square antiprisms are confirmed to be the driving building units for almost the entire size range. Three dominating fragmentation channels are observed, i.e. the loss of a tin atom for N < 12, a Sn-7 fragment for N < 19 and a Sn-10 fragment for N >= 19 with Sn-15 subunits constituting recurring geometric motifs for N > 20. The prolate-to-quasispherical structural transition is found to occur at 30 < N <= 40 and is analyzed with respect to the observed optical behavior taking quantum chemical calculations and the Mie-Gans theory into account. Limitations of the experimental approach to study the geometric and electronic structure of the clusters at elevated temperatures due to vibrational excitation is also thoroughly discussed.