Potential energy surface, dipole moment surface and the intensity calculations for the 10 mu m, 5 mu m and 3 mu m bands of ozone

摘要

Monitoring ozone concentrations in the Earth's atmosphere using spectroscopic methods is a major activity which undertaken both from the ground and from space. However there are long-running issues of consistency between measurements made at infrared (IR) and ultraviolet (UV) wavelengths. In addition, key O-3 IR bands at 10 mu m, 5 mu m and 3 mu m also yield results which differ by a few percent when used for retrievals. These problems stem from the underlying laboratory measurements of the line intensities. Here we use quantum chemical techniques, first principles electronic structure and variational nuclear-motion calculations, to address this problem. A new high-accuracy ab initio dipole moment surface (DMS) is computed. Several spectroscopically-determined potential energy surfaces (PESs) are constructed by fitting to empirical energy levels in the region below 7000 cm(-1) starting from an ab initio PES. Nuclear motion calculations using these new surfaces allow the unambiguous determination of the intensities of 10 mu m band transitions, and the computation of the intensities of 10 mu m and 5 mu m bands within their experimental error. A decrease in intensities within the 3 mu m is predicted which appears consistent with atmospheric retrievals. The PES and DMS form a suitable starting point both for the computation of comprehensive ozone line lists and for future calculations of electronic transition intensities. (C) 2018 The Authors. Published by Elsevier Ltd.