From Monomer to Bulk: Appearance of the Structural Motif of Solid Iodine in Small Clusters

• Published in: Journal of the American Chemical Society 2009-01, Vol.131 (3), p.1050-1056
• Main Authors: Hulkko, Eero, Kiljunen, Toni, Kiviniemi, Tiina, Pettersson, Mika
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja806537u

Formation of iodine clusters in a solid krypton matrix was studied using resonance Raman spectroscopy with a 1 cm−1 resolution. The clusters were produced by annealing of the solid and recognized by appearance of additional spectral transitions. Two distinct regions, red-shifted from the fundamental vibrational wavenumber of the isolated I2 at 211 cm−1, were observed in the signal. The intermediate region spans the range 196−208 cm−1, and the ultimate region consists of two peaks at 181 and 190 cm−1 nearly identical to crystalline I2. The experimental results were compared to DFT-D level electronic structure calculations of planar (I2) n clusters (n = 1−7). The dimer, trimer, and tetramer structures, where the I2 molecule is complexed from one end, were found to exhibit vibrational shifts corresponding to the intermediate size clusters. The larger, bulklike shift appears when the iodine molecule is coordinated from two opposite directions as in the case of a pentamer and higher clusters. Starting from the pentamer, the structural motif of crystalline iodine is clearly recognized in the clusters.