Quantum chemical calculations on a selection of iodine-containing species (IO, OIO, INO3, (IO)2, I2O3, I2O4 and I2O5) of importance in the atmosphere
Quantum chemical calculations on a selection of iodine-containing species (IO, OIO, INO3, (IO)2, I2O3, I2O4 and I2O5) of importance in the atmosphere
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DOI：
10.1039/b715687c
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发表时间：
2008-01-01
影响因子：
3.3
通讯作者：
Plane, John M. C.
中科院分区：
文献类型：
--
作者：
Kaltsoyannis, Nikolas;Plane, John M. C.
用量子化学从头算和密度泛函方法研究了标题配合物的电子结构和几何结构。耦合集群计算在标量相对论（基组）水平上进行，并使用相对论密度泛函理论研究的数据的自旋轨道耦合的结果进行了校正。在298 K下的生成热（kJ mol（-1））为：IO 3 147.8，INO 3 33.1，OIO 110.1，I2 O3 64.0，I2 O 4 111.3，I2 O 5 33.0，IOIO 141.3，IOOI 179.9和OI（I）O 157.9。这些数据被用来得出一些结论，碘化学在海洋边界层的三个重要方面。(i)虽然IO自身反应产生不对称二聚体IOIO，但由于其寿命较短，这种物质不太可能在大气中发挥进一步的作用。(ii)INO 3足够稳定，可以解释IO和NO2之间的复合反应动力学，而I-2和NO3之间产生I + INO 3的反应几乎肯定是夜间碘氧化物的主要来源。(iii)较高的碘氧化物I2 O3和I2 O 5是非常稳定的分子，与OIO二聚体I2 O 4相反，OIO二聚体I2 O 4不太稳定，但仍应在海洋边界层中存活足够长的时间，以提供碘氧化物颗粒形成的构件。
The electronic and geometric structures of the title complexes are studied quantum chemically using ab initio and density functional approaches. Coupled cluster calculations at the scalar relativistic (basis set) level are performed, and the results are corrected for spin-orbit coupling using data from relativistic density functional theory studies. The heats of formation ( kJ mol(-1)) at 298 K are found to be: IO3 147.8, INO3 33.1, OIO 110.1, I2O3 64.0, I2O4 111.3, I2O5 33.0, IOIO 141.3, IOOI 179.9 and OI(I)O 157.9. These data are used to draw a number of conclusions regarding three important aspects of iodine chemistry in the marine boundary layer. (i) Although the IO self reaction produces the asymmetric dimer, IOIO, it is unlikely that this species plays a further role in the atmosphere as it is short-lived. (ii) INO3 is sufficiently stable to explain the kinetics of the recombination reaction between IO and NO2, and the reaction between I-2 and NO3 to produce I + INO3 is almost certainly the major source of iodine oxides at night. (iii) The higher iodine oxides I2O3 and I2O5 are very stable molecules, by contrast to the OIO dimer, I2O4, which is much less stable but which should still survive long enough in the marine boundary layer to provide a building block for iodine oxide particle formation.