VIBRATIONAL PREDISSOCIATION SPECTROSCOPY OF HCN CLUSTERS

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1987

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Ohio State University

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Abstract

Vibrational predissociation spectra of HCN clusters formed in a supersonic expansion were obtained in the C-H stretching region. An F-center laser was scanned in the low resolution mode ($\Delta \nu= 10 GHz$) while the decrease in molecular beam signal due to recoiling predissociation fragments was monitored using a liquid He cooled bolometer. The C-H stretching frequency is a sensisitive probe of cluster size and of monomer position within the cluster. As a result, the evolution of vibrational frequency shifts due to hydrogen bond formation may be followed from small cluster size (dimer, trimer) to large aggregates that exhibit a solid-like absorption feature. The vibrational energy shifts will be discussed with respect to normal mode analysis, electrostatic interactions and ab initio results. Also, the potential of $(HCN)_{n}$ complexes to provide a model system to explore the development of other properties as clusters grow from isolated molecules into condensed phases will be discussed.

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Author Institution: Department of Chemistry, Indiana University

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