AN IMPROVED METHOD FOR THE DIRECT COMPUTATION OF DIATOMIC CENTRIFUGAL DISTORTION CONSTANTS

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1987

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Ohio State University

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A new algorithm for the numerical solution of inhomogeneous second-order differential equations is applied to the perturbation theory calculation of centrifugal distortion constants in diatomic molecules. The new scheme is similar to that of Hutson and $Howard^{1,2}$ but entails a combined inward and outward generation of the solution, analogous to that which is used in the $Cooley^{3}$ routine for solving the analogous homogeneous equation. The matching at an intermediate point eliminates instabilities in the nonclassical regions and permits a straightforward extraction of the desired particular solution from the initial numerical solution, which contains a component of the homogeneous solution. Numerical tests suggest that this method is capable of greater precision and efficiency than existing methods. A ``computer movie'' will be used to illustrate the method.

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$^{1}$ J. M. Hutson and B. J. Howard, Mol. Phys. 41, 1113 (1980). $^{2}$ J. M. Hutson, J. Phys. B: At. Mol. Phys. 14, 851 (1981). $^{3}$ J. W. Cooley, Math. Comput, 15, 363 (1961).
Author Institution: Department of Chemistry, Vanderbilt University

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