Effects on Calculated Half-Widths and Shifts from the Line Coupling for Asymmetric-Top Molecules.

摘要

The refinement of the Robert-Bonamy formalism by considering the line coupling for linear molecules developed in our previous studies [Q. Ma, C. Boulet, and R. H. Tipping, J. Chem. Phys. 139, 034305 (2013); 140, 104304 (2014)] have been extended to asymmetric-top molecules. For H2O immersed in N2 bath, the line coupling selection rules applicable for the pure rotational band to determine whether two specified lines are coupled or not are established. Meanwhile, because the coupling strengths are determined by relative importance of off-diagonal matrix elements versus diagonal elements of the operator -iS1 -S2, quantitative tools are developed with which one is able to remove weakly coupled lines from consideration. By applying these tools, we have found that within reasonable tolerances, most of the H2O lines in the pure rotational band are not coupled. This reflects the fact that differences of energy levels of the H2O states are pretty large. But, there are several dozen strongly coupled lines and they can be categorized into different groups such that the line couplings occur only within the same groups. In practice, to identify those strongly coupled lines and to confine them into sub-linespaces are crucial steps in considering the line coupling. We have calculated half-widths and shifts for some groups, including the line coupling. Based on these calculations, one can conclude that for most of the H2O lines, it is unnecessary to consider the line coupling. However, for several dozens of lines, effects on the calculated half-widths from the line coupling are small, but remain noticeable and reductions of calculated half-widths due to including the line coupling could reach to 5%. Meanwhile, effects on the calculated shifts are very significant and variations of calculated shifts could be as large as 25%.