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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Properties of Complexes Formed by Na~+, Mg~(2+), and Fe~(2+) Binding with Benzene Molecules
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Properties of Complexes Formed by Na~+, Mg~(2+), and Fe~(2+) Binding with Benzene Molecules

机译：Na〜+，Mg〜（2+）和Fe〜（2+）与苯分子结合形成的配合物的性质

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A theoretical investigation was performed to study cation-π interactions in complexes of benzene (Bz) with cations, that is, M~(z+)(Bz)_n for M~(z+) = Na~+, Mg~(2+), Fe~(2+) and n = 1-3, using MP2 theory with the 6-31+G* and 6-311+ +G** basis sets and the DFT/(B3LYP and B3LYP-D)/6-311++G** methods. Binding energies and structures of the complexes are reported. The splitting between the quintet and single states of the Fe~(2+) complexes was found to depend on the number of benzene molecules in the complex and the complex's structure. All of the M~(z+)(Bz) complexes prefer a half-sandwich geometry. A geometry with the cation sandwiched between the two benzene rings was found for the M~(z+)(Bz)_2 complexes, with the benzene rings either in an eclipsed or staggered conformation. An approximate cyclic structure, with the cation at its center, was found for three benzene molecules interacting with the cation. The cation-benzene binding energy is substantial and equal to 22, 108, and 151 kcal/mol for the Na~+(Bz), Mg~(2+)(Bz), and Fe~(2+)(Bz) complexes, respectively. The strength of the interaction of the cation with an individual benzene molecule decreases as the number of benzene molecules bound to the cation increases; for example, it is 108 kcal/mol for Mg~(2+)(Bz), but only 71 kcal/ mol for Mg~(2+)(Bz)_3. There is a range of values for the M~(z+)(Bz)_n intermolecular vibrational frequencies; for example, they are ～230-360 and ～10-330 cm~(-1) for the Mg~(2+)(Bz) and Mg~(2+)(Bz)3 complexes, respectively. Binding of the cation to benzene both red and blue shifts the benzene vibrational frequencies. This shifting is larger for the Mg~(2+) and Fe~(2+) complexes, as compared to those for Na~+, as a result of the former's stronger cation-benzene binding. The present study is an initial step to understand the possible importance of cation-π interactions for polycyclic aromatic hydrocarbon aggregation processes during soot formation.
机译：进行了理论研究以研究苯（Bz）与阳离子的络合物中的阳离子-π相互作用，即M〜（z +）= Na〜+，Mg〜（2+）的M〜（z +）（Bz）_n ，Fe〜（2+）和n = 1-3，使用MP2理论，具有6-31 + G *和6-311 + + G **基集，以及DFT /（B3LYP和B3LYP-D）/ 6- 311 ++ G **方法。报道了配合物的结合能和结构。发现Fe〜（2+）配合物的五重态和单态之间的分裂取决于配合物中苯分子的数量和配合物的结构。所有的M〜（z +）（Bz）络合物都偏爱半夹心几何形状。对于M〜（z +）（Bz）_2配合物，发现阳离子夹在两个苯环之间的几何结构，苯环呈偏光或交错构型。对于三个苯分子与阳离子相互作用，发现了一个以阳离子为中心的近似环状结构。对于Na〜+（Bz），Mg〜（2 +）（Bz）和Fe〜（2 +）（Bz）络合物，阳离子-苯的结合能很高，等于22、108和151 kcal / mol。 ， 分别。阳离子与单个苯分子的相互作用强度随与阳离子结合的苯分子数量的增加而降低;例如，Mg〜（2 +）（Bz）为108 kcal / mol，而Mg〜（2 +）（Bz）_3只有71 kcal / mol。 M〜（z +）（Bz）_n的分子间振动频率有一个范围。例如，Mg〜（2 +）（Bz）和Mg〜（2 +）（Bz）3配合物分别为〜230-360和〜10-330 cm〜（-1）。阳离子与苯的结合红色和蓝色都会改变苯的振动频率。 Mg〜（2+）和Fe〜（2+）配合物的转移比Na〜+大，这是由于前者更强的阳离子-苯结合。本研究是了解碳烟形成过程中阳离子-π相互作用对多环芳烃聚集过程可能的重要性的第一步。

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