Recent theoretical work by Kumar and Francisco suggested that the high reactivity of Criegee intermediates (CIs) could be utilized for designing efficient carbon capture technologies. Because the anti-CH3CHOO + CO2 reaction has the lowest barrier in their study, we chose to investigate it experimentally. We probed anti-CH3CHOO with its strong UV absorption at 365 nm and measured the rate coefficient to be <= 2 x 10(-17) cm(3) molecule(-1) s(-1) at 298 K, which is consistent with our theoretical value of 2.1 x 10(-17) cm(3) molecule(-1) s(-1) at the QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) level but inconsistent with their results obtained at the M06-2X/aug-cc-pVTZ level, which tends to underestimate the barrier heights. The experimental result indicates that the reaction of a Criegee intermediate with atmospheric CO2 (400 ppmv) would be inefficient (k(eff) < 0.2 s(-1)) and cannot compete with other decay processes of Criegee intermediates like reactions with water vapor (similar to 10(3) s(-1)) or thermal decomposition (similar to 10(2) s(-1)).
机构:
Univ Michigan, Dept Chem, Dept Atmospher Ocean & Space Sci, Ann Arbor, MI 48109 USAUniv Michigan, Dept Chem, Dept Atmospher Ocean & Space Sci, Ann Arbor, MI 48109 USA
机构:
Univ Naples Federico II, Complesso Univ Monte SantAngelo, Dipartimento Chim, Lab Struttura & Dinam Mol, I-80126 Naples, ItalyUniv Naples Federico II, Complesso Univ Monte SantAngelo, Dipartimento Chim, Lab Struttura & Dinam Mol, I-80126 Naples, Italy
机构:
Univ Michigan, Dept Chem, Dept Atmospher Ocean & Space Sci, Ann Arbor, MI 48109 USAUniv Michigan, Dept Chem, Dept Atmospher Ocean & Space Sci, Ann Arbor, MI 48109 USA
机构:
Univ Naples Federico II, Complesso Univ Monte SantAngelo, Dipartimento Chim, Lab Struttura & Dinam Mol, I-80126 Naples, ItalyUniv Naples Federico II, Complesso Univ Monte SantAngelo, Dipartimento Chim, Lab Struttura & Dinam Mol, I-80126 Naples, Italy