Scattering-State Spectroscopy as a Probe of Molecular Dynamics
| Autor: | P D Kleiber, K M Sando, and W C Stwalley |
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| Rok vydání: | 1993 |
| Předmět: | |
| Zdroj: | Annual Review of Physical Chemistry. 44:13-35 |
| ISSN: | 1545-1593 0066-426X |
| DOI: | 10.1146/annurev.pc.44.100193.000305 |
| Popis: | Traditional bound-state molecular spectroscopy has long served as a powerful probe of molecular structure and is increasingly being applied to the study of molecular dynamics. For example, the study of spectroscopic perturbations ( l ) can yield precise measurements of the strength of the nonadiabatic interactions that often determine the evolution of molecular processes. The spectroscopy of the continuum, or "scattering" states, of a transient coillision complex allows a more direct probe of bimolecular dynamics and is the subject of this review. Free-state absorption or emis sion spectroscopy yields direct information on the continuum structure, i.e. on the shape of the quasimolecular potential energy surfaces in the regions accessible by the Franck-Condon principle (2--4). Unlike bound state molecular spectroscopy, here the spectra are often unstructured, thus making interpretation difficult and somewhat perilous. In some cases, however, pronounced structure is observed in the spectra that may be clearly identified with features in the potential energy surfaces, such as local extrema or saddle points (2-4). Although it is rarely possible to invert the data directly (4), the spectra can provide a stringent test for model potential energy surfaces. Final scattering-state resolved measurements of the continuum "action" spectra are particularly sensitive to the dynamical evolution from the |
| Databáze: | OpenAIRE |
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