The Zeeman effect in doublet-quartet transitions in orthorhombic rotating molecules

Theoretical predictions on the effect of magnetic fields of variable strength on the rotational structure of doublet-quartet transitions in orthorhombic near symmetric top molecules are reported, with the assistance of computer simulations of line profiles. Low-field profiles are discussed, and it is shown that low-field linewidths are approximately equal to 2gβH|ΔJ ? ΔN| for transitions between states of any spin multiplicity. In a high field, transitions allowed by direct spin-orbit contamination of the combining states give rise to three lines with ΔM_s = 0, ±1, whereas two additional lines, with ΔM_s = ±2, are found if the combining states are appreciably contaminated also by indirect coupling to the active states, through intermediate levels. Computed Zeeman profiles are reported and discussed for several typical cases, with emphasis on the effects of different light polarizations. Prospectives of applicability are briefly outlined.