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- W2034390010 abstract "The 444 nm 201 bands of the à 2A′–X̃ 2A″ transition of the jet-cooled HP 35Cl and HP 37Cl radicals have been studied at high resolution using the pulsed electric discharge technique with a precursor mixture of PCl3 and H2. Spectra recorded with linewidths of ∼360 MHz revealed resolved hyperfine structure in both isotopomers arising from the excited state Fermi contact interaction of the unpaired electron with the magnetic moment of the P31 nucleus, with aF′=0.0641(10) cm−1 and 0.0636(31) cm−1 for HP 35Cl and HP 37Cl, respectively. No contribution from the ground state, or excited state contributions from the hydrogen or chlorine nuclei were resolved, confirming ab initio predictions that HPCl is a pπ radical in the X̃ state, and an sσ radical with a substantial contribution from the phosphorus 3s atomic orbital in the à state. The free atom comparison method has been used to estimate that the singly occupied molecular orbital in the excited state has 14% phosphorus 3s character." @default.
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- W2034390010 date "2004-07-02" @default.
- W2034390010 modified "2023-10-04" @default.
- W2034390010 title "Phosphorus hyperfine structure in the electronic spectrum of the HPCl free radical" @default.
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- W2034390010 doi "https://doi.org/10.1063/1.1758698" @default.
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