A theory of the broadening of the infrared absorption spectra of hydrogen-bonded species. I

Abstract

Abstract A theory of the intramolecular contributions to the broadening of the v(XH) absorption bands of hydrogen-bonded species is proposed, which is able to describe both vibrational predissociation and the formation of sum and difference bands. A formal method is developed for finding the wavefunctions and complex energy eigenvalues of quasi-stationary excited vibrational states of a linear triatomic system with realistic interactions. The theory is applied to the Me2O.HCl system. It is found that predissociation broadening is negligible. The calculation of combination band intensities, and of the spread in energy of terms within such bands, will be reported in a subsequent paper.