MARVEL Analysis of the Measured High-Resolution Rovibronic Spectra and Definitive Ideal-Gas Thermochemistry of the 16O2 Molecule

Abstract

Accurate, empirical rovibronic energy levels, with associated uncertainties, are determined for the lowest seven electronic states of the 16O2 molecule using the MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm. After careful analysis and validation of 30 671 rovibronic transitions (including 24 376 measured and 6295 artificial transitions), collected from 91 publications, 4279 empirical rovibronic energy levels are determined. The highly accurate empirical (MARVEL) energy database is then augmented with rovibronic energies obtained from accurate effective Hamiltonians for the lowest six electronic states, establishing a hybrid database containing 15 946 rovibronic energy levels. Based on this hybrid database, complete up to the first dissociation limit, 41 260 cm−1, an accurate temperature-dependent ideal-gas partition function, Qint(T), and some related thermochemical functions [isobaric heat capacity, Cpo(T), entropy, So(T), and (absolute) enthalpy, Ho(T)] are derived for 16O2 employing the direct-summation technique. All thermochemical functions are reported, in 1 K increments up to 5000 K, in the supplementary material to this paper.Accurate, empirical rovibronic energy levels, with associated uncertainties, are determined for the lowest seven electronic states of the 16O2 molecule using the MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm. After careful analysis and validation of 30 671 rovibronic transitions (including 24 376 measured and 6295 artificial transitions), collected from 91 publications, 4279 empirical rovibronic energy levels are determined. The highly accurate empirical (MARVEL) energy database is then augmented with rovibronic energies obtained from accurate effective Hamiltonians for the lowest six electronic states, establishing a hybrid database containing 15 946 rovibronic energy levels. Based on this hybrid database, complete up to the first dissociation limit, 41 260 cm−1, an accurate temperature-dependent ideal-gas partition function, Qint(T), and some related thermochemical functions [isobaric heat capacity, Cpo(T), entropy, So(T), and (absolute) enthalpy, Ho(T)] are derived for 16O2 em...