dc.creator Tao, C. en_US dc.creator Ebben, C. en_US dc.creator Ko, H. T. en_US dc.creator Reid, S. A. en_US dc.creator Wang, Z. en_US dc.creator Sears, T. J. en_US dc.date.accessioned 2009-07-29T12:58:08Z dc.date.available 2009-07-29T12:58:08Z dc.date.issued 2009 en_US dc.identifier 2009-TF-05 en_US dc.identifier.uri http://hdl.handle.net/1811/38281 dc.description M.~K.~Gilles, K.~M.~Ervin, J.~Ho, and W.~C.~Lineberger, J.~Phys.~Chem. 96, 1130 (1992). en_US dc.description Author Institution: Department of Chemistry, Marquette University, Milwaukee, WI 53233; Department of Chemistry, Brookhaven National Laboratory, Upton, NY 11973 en_US dc.description.abstract Among the triatomic halocarbenes, only the iodocarbenes remain to be characterized. The search for these elusive species is motivated by a controversy regarding the multiplicity of the ground state. Photoelectron spectra of Lineberger and co-workers suggest a triplet ground state for CHI, at variance with recent $ab~ initio$ studies, which suggest a singlet ground state with a singlet-triplet gap of around 4 kcal mol$^{-1}$. In this work, we have succeeded in finding the spectra of CHI and its deuterated isotopomer using pulsed discharge jet spectroscopy. Rotationally resolved fluorescence excitation spectra are consistent with a singlet-singlet transition, and the derived rotational constants are in good agreement with theoretical predictions. Single vibronic level emission spectra confirm a singlet multiplicity for the ground state, and reveal extensive mixing of the singlet and triplet levels at higher energy. We are able to set a lower limit on the singlet-triplet gap of 4.1 kcal mol$^{-1}$, in excellent agreement with theory. Extrapolation of the observed bending levels for CHI and CDI to a common origin suggests that the origin of the $A$^{1}A^{\prime\prime}$state lies near 10 500 cm$^{-1}\$, and we will report on high resolution measurements near the electronic origin made at Brookhaven National Laboratory. en_US dc.language.iso English en_US dc.publisher Ohio State University en_US dc.title FINDING THE ELUSIVE IODOCARBENE: FLUORESCENCE EXCITATION AND SINGLE VIBRONIC LEVEL EMISSION SPECTROSCOPY OF CHI en_US dc.type Article en_US
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