The Pitzer Free Rotor Model for Nondegenerate Modes:  Application to the Long-Range Behavior of Halogen Radical Reactions with Substituted Olefins

2003 ◽  
Vol 107 (22) ◽  
pp. 4483-4489 ◽  
Author(s):  
Mohamed Kharroubi ◽  
Pascal de Sainte Claire
Keyword(s):  
Long Range ◽  
Radical Reactions ◽  
Rotor Model ◽  
Halogen Radical

scholarly journals Bichromatic Photoassociation Spectroscopy for the Determination of Rotational Constants of Cs2 0 u + Long-Range State below the 6S1/2 + 6P1/2 Asymptote

Molecules ◽  
2020 ◽  
Vol 25 (17) ◽  
pp. 3963
Author(s):  
Jizhou Wu ◽  
Jie Ma ◽  
Yuqing Li ◽  
Wenliang Liu ◽  
Peng Li ◽  
...  
Keyword(s):  
Long Range ◽  
Spectroscopic Technique ◽  
Rigid Rotor ◽  
Simple Analysis ◽  
Rotational Constants ◽  
Vibrational Levels ◽  
Photoassociation Spectroscopy ◽  
Rotor Model ◽  
Good Agreement

This article demonstrates new observation of the high-resolution ro-vibrational bichromatic photoassociation spectra (BPAS) of Cs2 in the 0u+ long-range state below the asymptotes 6S1/2 + 6P1/2. By combining with a modulation spectroscopic technique, precise references of the frequency differences have been engineered through the BPAS, with which the rotational constants of low-lying vibrational levels of the Cs20u+ long-range state have been accurately determined by fitting the frequency differences to the non-rigid-rotor model. The rotational constants for the newly observed seven ro-vibrational levels are summarized and disagreement for the level ῦ = 498 is clarified. The rotational constants of different vibrational levels demonstrate strong perturbations of the related energy structures. A simple analysis is performed and shows good agreement with experimental results.

Long-range 13C,1H and 13C,19F coupling constants as indicators of the conformational properties of 4-fluoroanisole, 2,3,5,6-tetrafluoroanisole, and pentafluoroanisole

1984 ◽  
Vol 62 (8) ◽  
pp. 1592-1597 ◽  
Author(s):  
Ted Schaefer ◽  
Reino Laatikainen ◽  
Timothy A. Wildman ◽  
James Peeling ◽  
Glenn H. Penner ◽  
...  
Keyword(s):  
Long Range ◽  
Methoxy Group ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Dynamic Nmr ◽  
Methyl Group ◽  
Conformational Properties ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Rotor Model

Long-range spin–spin coupling constants over six bonds between 13C nuclei in the methyl group and ring protons or 19F nuclei in the para position are reported for 4-fluoroanisole, 2,3,5,6-tetrafluoroanisole, and pentafluoroanisole in solution. The couplings are σ–π electron mediated, as indicated by INDO MO FPT computations and by measurements on anisole, 2,6-dibromoanisole, 2,6-dichloroanisole, 2,6-dibromo-4-fluoroanisole, and 2,6-dibromo-4-methylanisole. On the basis of the measured coupling magnitudes and a hindered rotor model, it is concluded that the barrier to internal rotation about the [Formula: see text] bond in 4-fluoroanisole lies near 6 kcal/mol, is nearly zero in the tetrafluoroanisole, and is somewhat less than 1 kcal/mol in the pentafluoroanisole. In the latter, the preferred conformation is that in which the methoxy group lies in a plane perpendicular to the pentafluorophenyl plane. Some inconclusive dynamic nmr experiments on anisole, including T1ρ measurements, are briefly discussed.

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