A problem of gauge for matterndash;radiation interaction in calculations of intensities of vibrational transitions

摘要

A theory of absolute intensities of molecular vibrational transitions is formulated in terms of theTmatrix formalism of scattering theory. It is shown that the problem of the selection of the lsquo;lsquo;velocityrsquo;rsquo; (Amacr;thinsp;sdot;thinsp;pmacr;) gauge or the lsquo;lsquo;lengthrsquo;rsquo; (Emacr;thinsp;sdot;thinsp;rmacr;) gauge for description of the matterndash;radiation interaction in vibrational transitions is determined by the choice of the description of molecular eigenstates. The resulting consequences for radiationless transitions theory in polyatomic molecules are indicated.