Rydberg Fingerprint Spectroscopy of Hot Molecules: Structural Dispersion in Flexible Hydrocarbons
| Autor: | Job D. Cardoza, Michael P. Minitti, Peter M. Weber |
|---|---|
| Rok vydání: | 2006 |
| Předmět: |
Molecular Structure
Propylamines Chemistry Spectrum Analysis Temperature Degrees of freedom (physics and chemistry) Photoionization Butylamines Sensitivity and Specificity Vibration Molecular physics Hydrocarbons Piperazines Spectral line symbols.namesake Molecular geometry Rydberg formula symbols Molecule Physical and Theoretical Chemistry Atomic physics Spectroscopy Excitation |
| Zdroj: | The Journal of Physical Chemistry A. 110:10212-10218 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp062539a |
| Popis: | We explore how structural dispersion in flexible hydrocarbon chain molecules at very high temperatures is reflected in the photoionization spectra of Rydberg levels. The spectra of N,N-dimethylisopropanamine, N,N-dimethyl-1-butanamine, N,N-dimethyl-2-butanamine, N,N-dimethyl-3-hexanamine, and 1,4-dimethylpiperazine, taken at effective vibrational temperatures of 700-1000 K, show well-resolved features stemming from the 3p and 3s Rydberg states. The line shapes observed in molecules with internal rotation degrees of freedom show that multiple structures are populated. Following up on the discovery that low-lying Rydberg states provide sensitive fingerprints of molecular structures, this work supports Rydberg fingerprint spectroscopy as a tool to probe structural details of molecules in the presence of complex energy landscapes and at high vibrational temperatures. A simple model accounts for the sensitivity of Rydberg fingerprint spectroscopy to the molecular shape, as well as the relative insensitivity of the spectra toward vibrational excitation. |
| Databáze: | OpenAIRE |
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