THE CALCULATION OF CENTRIFUGAL DISTORTION IN POLYATOMIC MOLECULES

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1952

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Ohio State University

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The various methods which have been used to approximate the effect of centrifugal distortion on rotational energy levels will be reviewed. The first efforts were essentially classical but can be shown to be useful under certain conditions. The quantum-mechanical operator, with fourth-power terms in the components of angular momentum, gives a secular equation for asymmetric rotors which is laborious to utilize but is readily applicable to symmetric rotors. Recently a general approximate solution of the secular equation has been derived which reduces the labor required. In special cases terms in the operator of sixth degree in the angular-momentum components may be required but then anharmonicity corrections will enter the coefficients. The calculation of the coefficients from molecular force constants is difficult but has recently been somewhat simplified. These developments make it hopeful that microwave spectra will provide a new source of molecular force constants.

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Author Institution: Chemistry Department, Harvard University

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