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Author Dai, Zuyang ♦ Gao, Shuming ♦ Wang, Jia ♦ Mo, Yuxiang
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ CATIONS ♦ COUPLING ♦ ENERGY LEVELS ♦ IONIZATION ♦ KINETIC ENERGY ♦ METHANOL ♦ MOLECULES ♦ PHOTOELECTRON SPECTROSCOPY ♦ PHOTONS
Abstract The torsional energy levels of CH{sub 3}OH{sup +}, CH{sub 3}OD{sup +}, and CD{sub 3}OD{sup +} have been determined for the first time using one-photon zero kinetic energy photoelectron spectroscopy. The adiabatic ionization energies for CH{sub 3}OH, CH{sub 3}OD, and CD{sub 3}OD are determined as 10.8396, 10.8455, and 10.8732 eV with uncertainties of 0.0005 eV, respectively. Theoretical calculations have also been performed to obtain the torsional energy levels for the three isotopologues using a one-dimensional model with approximate zero-point energy corrections of the torsional potential energy curves. The calculated values are in good agreement with the experimental data. The barrier height of the torsional potential energy without zero-point energy correction was calculated as 157 cm{sup −1}, which is about half of that of the neutral (340 cm{sup −1}). The calculations showed that the cation has eclipsed conformation at the energy minimum and staggered one at the saddle point, which is the opposite of what is observed in the neutral molecule. The fundamental C–O stretch vibrational energy level for CD{sub 3}OD{sup +} has also been determined. The energy levels for the combinational excitation of the torsional vibration and the fundamental C–O stretch vibration indicate a strong torsion-vibration coupling.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2014-10-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 141
Issue Number 14


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