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UV spectroscopy of perylene-CO van der Waals complexes

✍ Scribed by Craig L. Perkins; Elizabeth Perez; Kenneth M. Beck

Publisher: Elsevier Science
Year: 1992
Tongue: English
Weight: 771 KB
Volume: 199
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(92)87025-k

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✦ Synopsis

A preliminary study of perylene-CO van der Waals complexes has been conducted. The spectroscopy of the major in-plane and out-of-plane features ofthe I : 1 and 1:2 perylene-CO aggregates hasbeen analyzed. Little perturbation to the G 'butterfly" outof-plane mode is seen in the complex, indicating that the CO moiety may be centered above the perylene plane. An energy shift of -82.5 and -81.9 cm-' is observed for 1: 1 complexes associated with the @ and 4 modes, respectively, of perylene. An electro static perturbation model is used to estimate the ground state well depth and intermolecular separation of 1: 1 perylen&O as D:=865cm-'andr,=3.4k

1. Intradnction

Current interest in isolated molecular clusters includes studies of structure, excitation, energy transfer, solvation effects, and unique features of phase transitions in smaller aggregates. Intermolecular potentials in these smaller clusters tend to be anisotropic [ 1 ] and may act as analogs to surface adsorption phenomena. The binding parameters in isolated clusters synthesized in the gas phase, as an example, may mimic active surface sites and give added insight into their interfacial chemistry.

Two related approaches have been taken to clarify cluster properties. The "small-molecule" approach involves high and very high resolution spectroscopy that affords information on the symmetry, structure, transition state, and potential energy surfaces of molecules and simple clusters all of which elucidate dissociative dynamics and intermolecular interactions. Analytic forms allow modelling of molecular dynamics and chemical transformation. The "largecluster" method utilizes small molecule and cluster data to elaborate trends in chemical and physical properties with increasing complex size and solva-

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