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首页> 外文会议>International Symposium on Combustion; 20060805-11; University of Heidelberg(DE) >Metal ion-molecule kinetics at combustion temperatures: The reaction of Ca~+ with O_2
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Metal ion-molecule kinetics at combustion temperatures: The reaction of Ca~+ with O_2

机译：燃烧温度下的金属离子分子动力学：Ca〜+与O_2的反应

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The high-temperature photochemistry (HTP) technique, previously used for reactions of neutral species, has been adapted to the study of atomic metal ion-molecule reactions. Ca~+ ions were generated by 193 nm multi-photon photolysis of calcium acetyl acetonate and its pyrolysis fragments. The relative ion concentrations were monitored by laser-induced fluorescence at 393.4 nm. Ar was used as the bath gas. The data for the Ca~+ + O_2 + M → CaO_2~+ + M association reaction (1) are fitted by k_1(907-1425 K) = 3.5 × 10~(-32) exp(+3161 K/T) cm~6 molecule~(-2) s~(-1). Combining with an approximate k_1(296 K) value in the literature leads to k_1(296-1425 K) = 5.8 × 10~(-22) (T/K)~(-2.9) exp(-601 K/T) cm~6 molecule~(-2) s~(-1). Over much of the observed temperature range reaction (1) has much smaller rate coefficients than the corresponding neutral Ca association reaction. Reaction (1) is shown to behave very similarly to the O_2 association reaction with neutral K atoms, with which Ca~+ is iso-electronic. This suggests that the initial step is ion-pair complex formation of the superoxide Ca~(2+)(O_2)~-, which is also consistent with results from density functional calculations. The k_1 values are rationalized via Troe's unimolecular formalism, which leads to good accord with the experiments.
机译：以前用于中性物质反应的高温光化学（HTP）技术已适应于原子金属离子分子反应的研究。乙酰丙酮钙及其热解片段的193 nm多光子光解产生Ca〜+离子。相对离子浓度通过激光诱导的393.4 nm荧光进行监测。 Ar被用作浴气体。 Ca〜+ + O_2 + M→CaO_2〜+ + M缔合反应（1）的数据拟合为k_1（907-1425 K）= 3.5×10〜（-32）exp（+3161 K / T）cm 〜6分子〜（-2）s〜（-1）。结合文献中的近似k_1（296 K）值可得出k_1（296-1425 K）= 5.8×10〜（-22）（T / K）〜（-2.9）exp（-601 K / T）cm 〜6分子〜（-2）s〜（-1）。在观察到的大部分温度范围内，反应（1）的速率系数比相应的中性Ca缔合反应小得多。反应（1）表现出与中性K原子的O_2缔合反应非常相似的反应，其中Ca〜+是等电的。这表明，第一步是离子对络合物形成超氧化物Ca〜（2 +）（O_2）〜-，这也与密度泛函计算的结果一致。通过Troe的单分子形式主义使k_1值合理化，这与实验非常吻合。

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