Nascent PO(X 2Π) E,V,R,T excitations from collision‐free IR laser photolysis: Specificity toward the PO(X 2Π1/2) spin‐orbit state
| Autor: | Jim‐Son Chou, David S. Sumida, Curt Wittig |
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| Rok vydání: | 1985 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 82:1376-1384 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.448460 |
| Popis: | PO (X 2Π) is produced via the collision‐free infrared multiple photon dissociation (IRMPD) of volatile organophosphorous molecules, and is detected by two‐frequency two‐photon ionization, using the B 2Σ+ state to provide a spectral signature from which X 2Π populations are obtained. Sequential dissociations occur during the IR laser photolysis, in which nascent fragments continue to undergo IRMPD, and PO (X 2Π) accrues from a series of bond fission reactions. Nascent vibrational, rotational, and translational excitations are in sensible accord with this mechanism, except for a few rotational states near J=19.5. Unlike the nuclear degrees of freedom, the PO (X 2Π) spin‐orbit states are populated quite selectively. The 2Π3/2 state, lying only 224 cm−1 above the 2Π1/2 ground state, contains only ∼11% of the population, compared to 34% for a 300 K sample. This result is unambiguous; it persists with all precursors, laser fluences, etc., and is verified by comparisons to spectra obtained using a microwave disc... |
| Databáze: | OpenAIRE |
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