High resolution ro–vibrational analysis of molecules in doublet electronic states: the ν1 fundamental of chlorine dioxide (16O35Cl16O) in the X2B1 electronic ground state

Autor: Martin Quack, Kirill B Berezkin, Olga Vasilievna Gromova, Elena Sergeevna Bekhtereva, C. Sydow, Sigurd Bauerecker, O.N. Ulenikov
Rok vydání: 2021
Předmět:
Zdroj: Physical Chemistry Chemical Physics. 23:4580-4596
ISSN: 1463-9084
1463-9076
Popis: We report the spectrum of the ν1 fundamental of chlorine dioxide centered in the infrared atmospheric window at 945.592 cm-1 measured with essentially Doppler limited resolution at an instrumental line width of 0.001 cm-1 using the Zurich prototype ZP2001 Bruker IFS 125 HR Fourier transform infrared spectrometer. The ro-vibrational line analysis is carried out with an improved effective Hamiltonian and a newly developed computer code ROVDES for the ro-vibrational spectra of open-shell free radical molecules including spin-rotation interactions. Accurate values of rotational, centrifugal and spin-rotational parameters were determined for 16O35Cl16O in the vibronic ground state X2B1 from more than 3500 ground state combination differences. The 7239 assigned transitions for the ν1 fundamental with Nmax = 76 and Kmaxa = 26 provide a set of 32 accurate effective Hamiltonian parameters for the ν1 fundamental (v1v2v3) = (100) (21 rotational and centrifugal distortion parameters and 11 spin-rotational interaction parameters). This effective Hamiltonian (A - reduction and Ir - representation) reproduces 1703 upper state energies from the experiment with a root-mean-square deviation drms = 1.67 × 10-4 cm-1 and the 7239 transition wavenumbers with drms = 3.45 × 10-4 cm-1. Our results provide a considerable improvement over previous results with which we compare and should provide a benchmark for theoretical studies with applications to atmospheric spectroscopy and laser chemistry, which are discussed in relation to our spectra.
Databáze: OpenAIRE
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