Small hydrogen bonded molecular clusters of HCN have been investigated in CCl4 solutions and in solid Ar, N2, and CCl4 matrices by means of FTIR spectroscopy in the spectral range 4000 ‐ 10 cm−1. In Ar and N2 matrices aggregated species up to tetramers can readily be identified. HCN dimers have been formed selectively in these matrices by photofragmentation of s‐tetrazine. Both the intra‐ and intermolecular modes observed are consistent with a linear dimer structure. Photolysis of s‐triazine generated selectively HCN trimers, obviously with a cyclic structure stabilized by the matrix cage. On the other hand, linear trimers and tetramers were detected in Ar and N2 matrices after time and temperature controlled diffusion of isolated monomers and dimers, respectively. Linear configurations are also typical for the HCN aggregation in CCI4. In liquid solutions no HCN clusters larger than dimers were observed. In the plastic crystalline phase of CCl4, on the other hand, dimers and trimers are present. Only in the crystalline CCl4 phase larger HCN chains of unspecified length may be formed.
Clusters j Matrix Isolation j Molecular Interactions / Neutron Scattering j Spectroscopy, InfraredInelastic neutron scattering has been applied for the first time to the study of matrix isolated species whose thermodynamically stable phase under normal conditions is the liquid. The aims of these investigations, which are complemented by far infrared studies, are to explore the aggregational behaviour of acetonitrile and the intermolecular dynamics of the respective aggregates in low temperature matrices of solid Ar and CC4. The only aggregate observed, using a variety of different spectroscopic techniques and diverse experimental conditions, is an antiparallel dimer. In contrast to the external intermolecular modes of this aggregate, which were not accessible by vibrational spectroscopy, the internal modes could be described and assigned.
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