Full quantum calculations of the line shape for H2O perturbed by Ar at temperatures from 20 to 300 K

Abstract

This work theoretically studied the spectral line shape of H2O perturbed by Ar in the temperature range of 20–300 K for the pure rotational lines below 360 cm−1, as well as three lines (31, 2 ← 44, 1, 54, 2 ← 41, 3, and 73, 5 ← 60, 6) in the v2 band. In order to perform precise dynamical calculations at low collision energies, a full-dimensional long-range potential energy surface was constructed for the H2O–Ar system for the first time to correct the long range of our newly developed intermolecular potential energy surface. Subsequently, the six line-shape parameters (pressure-broadening and -shifting parameters, their speed dependencies, and the complex Dicke parameters) were determined from the generalized spectroscopic cross section by the full quantum time-independent close-coupling approach on this new potential energy surface. Our theoretical results are in good agreement with the available experimental observations. Furthermore, the influence of the speed-dependence and Dicke narrowing effects on the line contour was revealed by comparing the differences among the Hartmann–Tran, quadratic-speed-dependent Voigt, and Voigt profiles. The temperature dependence of each line-shape parameter was further parameterized using the triplet-power-law for three pure rotational 61, 6 ← 52, 3, 41, 4 ← 32, 1, and 31, 3 ← 22, 0 lines. These line-shape parameters will provide a comprehensive set of theoretical references for subsequent experimental measurements.