dc.creator Ishikawa, H. en_US dc.creator Nagao, C. en_US dc.creator Mikami, N. en_US dc.creator Field, R. W. en_US dc.date.accessioned 2006-06-15T19:03:56Z dc.date.available 2006-06-15T19:03:56Z dc.date.issued 1998 en_US dc.identifier 1998-RF-06 en_US dc.identifier.uri http://hdl.handle.net/1811/18919 dc.description $^{a}$ H. Ishikawa et al., J. Chem. Phys. 105, 7383 (1996). $^{b}$ C. Beek et al., J. Chem. Phys. 107, 9818 (1997). en_US dc.description Author Institution: Department of Chemistry, Graduate School of Science, Tohoku University; Department of Chemistry, Massachusetts Institute of Technology en_US dc.description.abstract Highly excited vibrational levels of HCP, in which bend-CP stretch polyads are the most fundamental vibrational structure, have been investigated by dispersed fluorescence and stimulated emission pumping spectroscopies. $HCP \longleftrightarrow CPH$ system is a prototype of the isomerization reaction of triatomic monohydride. HAB, that is the most simplest bond-breaking isomerization. Simulated by the experimental observation of vibrational levels with rotational constants (B-values) 5-10\% larger than other observed $leels,^{a}$ Schinke and coworkers noticed that these large-B levels were characterized by atypical nodal structures indicative of large amplitude motion along the minimum energy $HCP \longleftrightarrow CPH$ isomerization $path.^{b}$ Vibrational levels having such nodal structures can be referred to as isomerization'' levels. In order to elucidate the generation of the isomerization'' states, a global least squares fit, based on a traditional spectroscopic (algebraic) effective Hamiltonian polyad model, was carried out. An analysis of eigenvectors of the Hamiltonian matrix shows that all of the observed isomerization'' states belong to polyads and that the eigenvectors of this $H^{eff}$ model have the qualitatively distinct nodal structure first noticed by Schinke and coworkers. The isomerization'' states are not indicative of a breakdown of the polyad model; rather they are a natural consequence of this traditional spectroscopic model. en_US dc.format.extent 174563 bytes dc.format.mimetype image/jpeg dc.language.iso English en_US dc.publisher Ohio State University en_US dc.title SPECTROSCOPIC INVESTIGATION OF THE GENERATION OF ISOMERIZATION'' STATES OF HCP: EIGEN-VECTOR ANALYSIS OF THE BEND- CP STRETCH POLYAD en_US dc.type article en_US
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