Abstract

The infrared paradox is an inconsistency in the current derivation of the Einstein coefficient for vibrational excitations in molecular spectroscopy. A solution to the paradox is proposed by extending well established developments in the theory of atomic collisions to the case of vibrating molecules. When delay effects are unimportant, the new method does not require any change in the standard calculation of frequencies or intensities—only a reinterpretation of the nuclear wave functions. The improved formalism eliminates the problem of asymptotic couplings in molecular spectroscopy, as well as a basic difficulty in the usual picture of molecular structure.

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