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DISCOVERY OF THE ELECTRONIC SPECTRA OF HPS AND DPS

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/38076

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Title: DISCOVERY OF THE ELECTRONIC SPECTRA OF HPS AND DPS
Creators: Grimminger, Robert A.; Wei, Jie; Ellis, Blaine; Clouthier, Dennis J.; Wang, Zhong; Sears, Trevor
Issue Date: 2009
Abstract: The hitherto unknown electronic spectrum of the closed shell transient molecule HPS has been observed in the 685 - 846 nm region by laser-induced fluorescence and single vibronic level emission techniques. HPS (and DPS) were produced in a pulsed electric discharge jet using a precursor mixture of 3\% PH$_3$ and 1\% H$_2$S (or PD$_3$ and D$_2$S) in high pressure argon. The weak set of observed bands are assigned to the $\~A $^1$A^{\prime \prime}-\~X $^1$A^{\prime}$ electronic transition on the basis of chemical evidence, isotope shifts and the correspondence of the vibrational frequencies, excitation energy, and band contours with predictions based on our own high level {\em ab initio} calculations. Theory predicts that the HPS bond angle decreases on electronic excitation, contrary to expectations based on Walsh diagrams.
URI: http://hdl.handle.net/1811/38076
Other Identifiers: 2009-TJ-05
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