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Molecular beam photoionization studies of molecules and their van der Waals clusters

Thesis/Dissertation ·
OSTI ID:5903238

A new photoionization apparatus incorporating a supersonic molecular beam, a quadrupole mass spectrometer and a 3-m vacuum ultraviolet monochromator has been used to study the nitric oxide, carbon disulfide, carbonyl sulfide and acetylene molecules along with their van der Waals clusters. Using a wavelength resolution of 0.14 A (FWHM), photoionization efficiency curves were obtained for NO, CS/sub 2/, OCS, and C/sub 2/H/sub 2/ in the respective threshold regions and ionization energy determinations accurate to within 3 MeV were made. The autoionization structures resolved have led to new interpretations and assignments to Rydberg levels. Photoionization efficiency data for the clusters were obtained under lower resolution, typically 1.4 A (FWHM) and led to binding energy determinations of the cluster ions. Other thermochemical values were deducted from fragment appearance energies and sharp rises in ionization efficiencies. From the (CS/sub 2/)/sub 2/ fragment curves, relative reaction probabilities for the formation of the various product channels as a function of the Rydberg level n were determined for CS/sub 2/(V,n).CS/sub 2/ and the branching ratios were measured for the reaction CS/sub 2/(V,n) + CS/sub 2/. The shifts observed in the autoionization peaks of the triatomic molecules CS/sub 2/ and OCS due to clustering was investigated and a model is proposed which accounts for these characteristics. Ionization of the acetylene dimer and trimer resulted in clusters which could rearrange to form ions of a more stable configuration.

OSTI ID:
5903238
Country of Publication:
United States
Language:
English