The environmentally important free radical reaction of chlorinated methyl CHCl2 with NO2 was investigated by step-scan time-resolved FTIR （TR-FTIR） emission spectroscopy. Vibrationally excited products of CHClO, NO,...The environmentally important free radical reaction of chlorinated methyl CHCl2 with NO2 was investigated by step-scan time-resolved FTIR （TR-FTIR） emission spectroscopy. Vibrationally excited products of CHClO, NO, CO, and HCl are observed in the high-resolution IR emission spectra and three possible reaction channels are therefore elucidated. In particular, the product CO is newly detected and the product HCl is identified explicitly as a yield from the CHCl2＋NO2 reaction, taking advantage of the sensitive detection of HCl and CO with TR-FTIR. These results are of particular interests to understand the related realistic chemical processes including atmospheric photochemistry, biofuel combustion, waste destruction, and smoking fire.展开更多
Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental impor...Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions.In sharp contrast to the intensively studied parent molecule(CH_(2)OO)and the alkyl-substituted derivatives,the knowledge about the fluorinated analogue CF_(3)C(H)OO is scarce.By carefully heating the triplet carbene CF_(3)CH in an O2-doped Ar-matrix to 35 K,the elusive carbonyl oxide CF_(3)C(H)OO in syn-and anti-conformations has been generated and characterized with infrared(IR)and ultraviolet-visible(UV-vis)spectroscopy.The spectroscopic identification is supported by^(18)O-labeling experiments and quantum chemical calculations at the B3 LYP/6-311++G(3df,3pd)and MP2/6-311++G(2d,2p)levels.Upon the long-wavelength irradiation(λ>680 nm),both conformers of CF_(3)C(H)OO decompose to give trifluoroacetaldehyde CF_(3)C(H)O and simultaneously rearrange to the isomeric dioxirane,cyclic-CF_(3)CH(OO),which undergoes isomerization to the lowest-energy carboxylic acid CF_(3)C(O)OH upon UV-light excitation at 365 nm.The O_(2)-oxidation of CF_(3)CH via the intermediacy of CF_(3)C(H)OO and cyclic-CF_(3)CH(OO)might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF_(3)CHCl_(2)(HCFC-123)in the atmosphere.展开更多
基金Ⅴ. ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20733005 and No.20673126）, the National Basic Research Program of China （No.2007CB815200 and No.2007AA02Z116）, and the Chinese Academy of Sciences.
文摘The environmentally important free radical reaction of chlorinated methyl CHCl2 with NO2 was investigated by step-scan time-resolved FTIR （TR-FTIR） emission spectroscopy. Vibrationally excited products of CHClO, NO, CO, and HCl are observed in the high-resolution IR emission spectra and three possible reaction channels are therefore elucidated. In particular, the product CO is newly detected and the product HCl is identified explicitly as a yield from the CHCl2＋NO2 reaction, taking advantage of the sensitive detection of HCl and CO with TR-FTIR. These results are of particular interests to understand the related realistic chemical processes including atmospheric photochemistry, biofuel combustion, waste destruction, and smoking fire.
基金supported by the National Natural Science Foundation of China(Nos.22003010 and 22025301)
文摘Criegee intermediates(CIs),also known as carbonyl oxide,are reactive intermediates that play an important role in the atmospheric chemistry.Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions.In sharp contrast to the intensively studied parent molecule(CH_(2)OO)and the alkyl-substituted derivatives,the knowledge about the fluorinated analogue CF_(3)C(H)OO is scarce.By carefully heating the triplet carbene CF_(3)CH in an O2-doped Ar-matrix to 35 K,the elusive carbonyl oxide CF_(3)C(H)OO in syn-and anti-conformations has been generated and characterized with infrared(IR)and ultraviolet-visible(UV-vis)spectroscopy.The spectroscopic identification is supported by^(18)O-labeling experiments and quantum chemical calculations at the B3 LYP/6-311++G(3df,3pd)and MP2/6-311++G(2d,2p)levels.Upon the long-wavelength irradiation(λ>680 nm),both conformers of CF_(3)C(H)OO decompose to give trifluoroacetaldehyde CF_(3)C(H)O and simultaneously rearrange to the isomeric dioxirane,cyclic-CF_(3)CH(OO),which undergoes isomerization to the lowest-energy carboxylic acid CF_(3)C(O)OH upon UV-light excitation at 365 nm.The O_(2)-oxidation of CF_(3)CH via the intermediacy of CF_(3)C(H)OO and cyclic-CF_(3)CH(OO)might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF_(3)CHCl_(2)(HCFC-123)in the atmosphere.
