A set of accurate spectroscopic parameters for the detection of the atmospherically important HOC(O)O radical has been obtained by means of state-of-the-art ab initio computations. These include advanced coupled cluster treatments, involving both standard and explicitly correlated approaches, to correctly account for basis set incompleteness and core-valence effects. Geometric parameters for the X∼2A′ and Ã2A′′ states and, for the ground state only, vibrationally corrected rotational constants including quartic and sextic centrifugal distortion terms are reported. The infrared spectrum of the X∼2A′ state has been simulated in the 4000-400 cm-1wavenumber interval with an approach based on second order vibrational perturbation theory that allows accounting for anharmonic effects in both energies and intensities. Finally, the vibronic spectrum for the à ← X∼ transition has been calculated at three different temperatures in the 9000-3000 cm-1energy range with a time-independent technique based on the Franck-Condon approximation.

Puzzarini, C., Biczysko, M., Peterson, K.A., Francisco, J.S., Linguerri, R. (2017). Accurate spectroscopic characterization of the HOC(O)O radical: A route toward its experimental identification. THE JOURNAL OF CHEMICAL PHYSICS, 147(2), 024302-1-024302-10 [10.1063/1.4990437].

Accurate spectroscopic characterization of the HOC(O)O radical: A route toward its experimental identification

Puzzarini, Cristina;
2017

Abstract

A set of accurate spectroscopic parameters for the detection of the atmospherically important HOC(O)O radical has been obtained by means of state-of-the-art ab initio computations. These include advanced coupled cluster treatments, involving both standard and explicitly correlated approaches, to correctly account for basis set incompleteness and core-valence effects. Geometric parameters for the X∼2A′ and Ã2A′′ states and, for the ground state only, vibrationally corrected rotational constants including quartic and sextic centrifugal distortion terms are reported. The infrared spectrum of the X∼2A′ state has been simulated in the 4000-400 cm-1wavenumber interval with an approach based on second order vibrational perturbation theory that allows accounting for anharmonic effects in both energies and intensities. Finally, the vibronic spectrum for the à ← X∼ transition has been calculated at three different temperatures in the 9000-3000 cm-1energy range with a time-independent technique based on the Franck-Condon approximation.
2017
Puzzarini, C., Biczysko, M., Peterson, K.A., Francisco, J.S., Linguerri, R. (2017). Accurate spectroscopic characterization of the HOC(O)O radical: A route toward its experimental identification. THE JOURNAL OF CHEMICAL PHYSICS, 147(2), 024302-1-024302-10 [10.1063/1.4990437].
Puzzarini, Cristina; Biczysko, Malgorzata; Peterson, Kirk A.; Francisco, Joseph S.; Linguerri, Roberto*
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/624719
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