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Title:SPIN-ROTATION HYPERFINE SPLITTINGS AT MODERATE TO HIGH J VALUES IN METHANOL
Author(s):Xu, Li-Hong
Contributor(s):Mescheryakov, A. A.; Alekseev, E. A.; Ilyushin, V.; Lapinov, Alexander; GOLUBIATNIKOV, G Yu; Belov, Sergey; Hougen, Jon T.
Subject(s):Mini-symposium: High-Precision Spectroscopy
Abstract:In this talk we present a possible explanation, based on torsionally mediated proton-spin-overall-rotation interaction operators, for the surprising observation in Nizhny Novgorod several years agofootnote{G. Yu. Golubiatnikov, S. P. Belov, A. V. Lapinov, "chem{CH_3OH} Sub-Doppler Spectroscopy," (Paper MF04) and S.P. Belov, A.V. Burenin, G.Yu. Golubiatnikov, A.V. Lapinov, "What is the Nature of the Doublets in the E-Methanol Lamb-dip Spectra?" (Paper FB07), 68$^{th}$ International Symposium on Molecular Spectroscopy, Columbus, Ohio, June 2013.} of doublets in some Lamb-dip sub-millimeter-wave transitions between torsion-rotation states of E symmetry in methanol. These observed doublet splittings, some as large as 70 kHz, were later confirmed by independent Lamb-dip measurements in Kharkov. In this talk we first show the observed J-dependence of the doublet splittings for two b-type Q branches (one from each laboratory), and then focus on our theoretical explanation. The latter involves three topics: (i) group theoretically allowed terms in the spin-rotation Hamiltonian, (ii) matrix elements of these terms between the degenerate components of torsion-rotation E states, calculated using wavefunctions from an earlier global fit of torsion-rotation transitions of methanol in the v$_{t}$ = 0, 1, and 2 statesfootnote{Li-Hong Xu, J. Fisher, R.M. Lees, H.Y. Shi, J.T. Hougen, J.C. Pearson, B.J. Drouin, G.A. Blake, R. Braakman, "Torsion-Rotation Global Analysis of the First Three Torsional States (v$_{t}$ = 0, 1, 2) and Terahertz Database for Methanol," J. Mol. Spectrosc., $bf{251}$, 305-313, (2008).}, and (iii) least-squares fits of coefficients of these terms to about 35 experimentally resolved doublet splittings in the quantum number ranges of K = -2 to +2, J = 13 to 34, and v$_{t}$ = 0. Rather pleasing residuals are obtained for these doublet splittings, and a number of narrow transitions, in which no doublet splitting could be detected, are also in agreement with predictions from the theory. Some remaining disagreements between experiment and the present theoretical explanation will be mentioned.
Issue Date:24-Jun-15
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:ACS
Genre:CONFERENCE PAPER/PRESENTATION
Type:Text
Language:English
URI:http://hdl.handle.net/2142/79250
Date Available in IDEALS:2016-01-05


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