Calculation of the absolute photoionization cross-sections for C1–C4 Criegee intermediates and vinyl hydroperoxides

Abstract

Criegee Intermediates (CIs) and their isomer Vinyl Hydroperoxides (VHPs) are crucial intermediates in the ozonolysis of alkenes. To better understand the underlying chemistry of CIs and VHPs, progress has been made to detect and identify them by photoionization mass spectrometric experiments. Further reliable quantitative information about these elusive intermediates requires their photoionization cross sections. The present work systematically investigated the near-threshold absolute photoionization cross-sections for ten C1-C4 CIs and VHPs, i.e., formaldehyde oxide (CH2OO), acetaldehyde oxide (syn-/anti-CH3CHOO), acetone oxide ((CH3)2COO), syn-CH3-anti-(cis-CH=CH2)COO, syn-CH3-anti-(trans-CH=CH2)COO and vinyl hydroperoxide (CH2CHOOH), 2-hydroperoxypropene (CH2=C(CH3)OOH), syn-CH2 = anti-(cis-CH=CH2)-COOH, syn-CH2 = anti-(trans-CH=CH2)COOH. The adiabatic ionization energies (AIEs) were calculated at the DLPNO-CCSD(T)/CBS level with uncertainties of less than 0.05 eV. The calculated AIEs for C1-C4 CIs and VHPs vary from 8.75 to 10.0 eV with the AIEs decreasing as the substitutions increase. Franck-Condon factors were calculated with the double Duschinsky approximation and the ionization spectra were obtained based on the calculated ionization energies. Pure electronic photoionization cross sections are calculated by the frozen-core Hartree-Fock (FCHF) approximation. The final determined absolute cross sections are around 4.5-6 Mb for the first and second ionization of CIs and 15-25 Mb for VHPs. It is found that the addition of a methyl group or an unsaturated vinyl substitution for the CIs does not substantially change the absolute value of their cross sections.