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 × 10^–17 cm³ molecule^–1 s^–1 at 298 K, which is consistent with our theoretical value of 2.1 × 10^–17 cm³ 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 (∼10³ s^–1) or thermal decomposition (∼10² s^–1).

中文翻译：

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Criegee中间体对二氧化碳的反应活性

Kumar和Francisco的最新理论工作表明，Criegee中间体（CIs）的高反应活性可用于设计有效的碳捕集技术。因为抗-CH ₃ CHOO + CO ₂反应在他们的研究中具有最低的障碍，所以我们选择进行实验研究。我们在365 nm处检测到具有强紫外线吸收的抗-CH ₃ CHOO，并在298 K下测得的速率系数为≤2×10 ^–17 cm ³分子^–1 s ^–1，这与我们的理论值2.1× 10 ^–17 cm ³ 分子^–1 sQCISD（T）/ CBS // B3LYP / 6-311 + G（2d，2p）级别为^–1，但与M06-2X / aug-cc-pVTZ级别获得的结果不一致，这往往会低估障碍高度。实验结果表明，Criegee中间体与大气CO ₂（400 ppmv）的反应效率低（k _eff <0.2 s ^–1），并且不能与其他Criegee中间体的衰变过程竞争，例如与水蒸气的反应（〜10 ^3）。 s ^–1）或热分解（〜10 ² s ^–1）。