Infrared spectroscopy of nonclassical ions and their complexes
- Univ. of California, Berkeley, CA (United States)
This thesis describes an infrared spectroscopic study on the structures and dynamics of the nonclassical ions and their complexes, using ion trap vibrational predissociation spectroscopy. Chapter One provides an introduction to the experimental apparatus used in this work. Chapter Two describes the previous theoretical and experimental works on the carbonium ion CH5+ and infrared spectroscopic and theoretical works on CH5+. CH5+ was predicted to scramble constantly without possessing a stable structure. In Chapter Three, the infrared spectroscopy for the molecular hydrogen solvated carbonium ions CH5+(H2)n (n=1-6) in the frequency region of 2700-4200 cm-1 are presented and compared with the results of ab initio molecular dynamics simulation on CH5+(H2)n (n=0-3). The results suggested that the scrambling of CH5+ slowed down considerably by the stabilization effects of the solvent H2 molecules, and it was completely frozen out when the first three H2 molecules were bound to the core CH5+. Chapter Four presents the complete infrared spectra for the solvated carbonium ions, CH5+(A)x(B)y (A,B=H2, Ar, N2, CH4;x,y=0-5) in the frequency region of 2500-3200 cm-1. As the binding affinities of the solvent molecules and the number of the solvent molecules in the clusters increased, the scrambling of CH5+ slowed down substantially. The structures of the solvated carbonium ions and the evidence for rapid proton transfer in CH5+(CH4) were also presented. Chapter Five presents the vib-rotational spectrum for the H-H stretching mode of the silanium ion SiH5+. The results suggested that SiH5+ can be described as a complex of SiH3+ and a freely internally rotating H2, analogous to, but distinct from CH5+.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 29429
- Report Number(s):
- LBL-36702; ON: DE95008487; TRN: 95:002886
- Resource Relation:
- Other Information: TH: Thesis (Ph.D.); PBD: Jan 1995
- Country of Publication:
- United States
- Language:
- English
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