2018/02/12 by O. L. Polyansky, Oleg L. Polyansky, Nikolai F. Zobov +4 · 20 citations
Chemistry · Earth and Planetary Sciences · Physics and Astronomy · #Ab initio #Ab initio quantum chemistry methods #Atmospheric Ozone and Climate #Atmospheric chemistry and aerosols #Atomic physics #Chemistry #Computational physics #Dipole #Infrared #Line (geometry) #Molecular physics #Molecule #Moment (physics) #Optics #Ozone #Physics #Potential energy #Potential energy surface #Spectroscopy and Laser Applications #Transition dipole moment #physics.ao-ph #physics.chem-ph
paper · pdf · doi:10.1016/j.jqsrt.2018.02.018
published in Journal of Quantitative Spectroscopy and Radiative Transfer 210, 127-135 (Elsevier BV) · 36 pages, 1 figure, 5 tables
openalex publication_date 2018/02/12 · arxiv created 2018/02/27 · openalex created_date 2018/03/06 · arxiv updated 2018/04/22 · openalex updated_date 2026/08/05
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 µm, 5 µm and 3 µm 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 µm band transitions, and the computation of the intensities of 10 µm and 5 µm bands within their experimental error. A decrease in intensities within the 3 µm 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.