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- W2134232783 abstract "According to the simple theory of the rigid rotator and harmonic oscillator, the coefficients of J(J+1) and (v+½) in the energy should be inversely proportional to respectively the reduced mass and the square root thereof. Actually various small corrections, important only in compounds containing hydrogen or deuterium, make the mass dependence slightly different, and hence, at least in principle, explain why spectroscopic observations may yield slightly incorrect mass ratios for isotopes. The corrections are due to four causes (a) anharmonicity, (b) interaction between vibration and electronic motion even when perturbations between different electronic states are neglected, (c) L uncoupling or in other words perturbations between states differing by one unit in Λ, (d) interaction between states of equal Λ. The formulas for the various corrections are collected—some old, some new or more exact than previously. The relative magnitudes of the different effects are estimated. Incidentally, perturbations between states of equal Λ are studied in general. They should increase in intensity with the vibrational quantum number v, all other things being equal, in contrast to the perturbations due to L uncoupling, which increase with J. The electronic isotope shift, or displacement in the absolute value of the energy is also treated. Here the correction for the motion of the center of gravity of the molecule, usually neglected, is shown to be fully coordinate in importance with other terms. Shifts for ultraviolet lines of hydrogen are calculated with the Wang wave functions, and agree qualitatively with experiment. A concluding section is included on the mean square angular momentum of H2, which enters in connection with diamagnetism and the Stern-Gerlach effect." @default.
- W2134232783 created "2016-06-24" @default.
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- W2134232783 date "1936-06-01" @default.
- W2134232783 modified "2023-09-26" @default.
- W2134232783 title "On the Isotope Corrections in Molecular Spectra" @default.
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- W2134232783 doi "https://doi.org/10.1063/1.1749853" @default.
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