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Title:VIBRATIONALLY-RESOLVED KINETIC ISOTOPE EFFECTS IN THE PROTON-TRANSFER DYNAMICS OF GROUND-STATE TROPOLONE
Author(s):Chew, Kathryn
Contributor(s):Vaccaro, Patrick; Vealey, Zachary
Subject(s):Dynamics/Kinetics/Ultrafast
Abstract:The vibrational and isotopic dependence of the hindered (tunneling-mediated) proton-transfer reaction taking place in the ground electronic state (textit{~{X}$^{1}$}{A}$_{1}$) of monodeuterated tropolone (TrOD) has been explored under ambient (bulk-gas) conditions by applying two-color variants of resonant four-wave mixing (RFWM) spectroscopy in conjunction with polarization-resolved detection schemes designed to alleviate spectral complexity and facilitate rovibrational assignments. Full rotation-tunneling analyses of high-resolution spectral profiles acquired for the fundamental and first-overtone bands of a reaction-promoting O$-$D$cdots$O deformation/ring-breathing mode, nub{36}(a$_{1}$), were performed, thereby extracting refined structural and dynamical information that affords benchmarks for the quantitative interpretation of tunneling-induced signatures found in long-range scans of textit{~{X}$^{1}$}{A}$_{1}$ vibrational levels residing below mbox{$it{E}$$^{tilde{X}}_{vib}$ = 1700 wn}. Observed kinetic isotope effects, which reflect changes in both reaction kinematics and vibrational displacements, will be discussed, with high-level quantum-chemical calculations serving to elucidate state-resolved propensities for proton transfer in TrOH and TrOD.
Issue Date:23-Jun-15
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:ACS
Genre:CONFERENCE PAPER/PRESENTATION
Type:Text
Language:English
URI:http://hdl.handle.net/2142/79463
Date Available in IDEALS:2016-01-05


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