Laboratorio de Química Computacional y Teórica, Facultad de Química, Universidad de La Habana, 10400 Havana, Cuba.
J Mol Graph Model. 2010 Jun;28(8):746-54. doi: 10.1016/j.jmgm.2010.01.012. Epub 2010 Feb 6.
The behavior of O(2) molecule in models of acid aluminosilicate sites on any kind of material was investigated using reliable QM ab initio calculations. The triplet-singlet energy gap of isolated O(2) was calculated at confident levels of theory with different basis sets as a reference. Models of aluminosilicate active sites interacting with oxygen in their singlet and triplet electronic states were considered for two kinds of O(2) arrangements. Geometry optimizations were performed on both non-corrected and corrected BSSE potential energy surfaces, realizing that good modeling of heavy atom-hydrogen interactions is sensitive to BSSE corrections during these processes. Energies were further evaluated at higher level of theory to test tendencies. Singlet oxygen appears more attractive to active aluminosilicate sites than those calculated with triplet oxygen, indicating a source of oxidative efficiency for designed nanostructures containing such molecular residues. It was clearly seen that aluminosilicate groups, appearing ubiquitously in several materials, could reduce the O(2) triplet-singlets energy gap by at least 10 kJ/mol. Some elegant features of oxygen interactions with such sites were further analyzed by means of the atoms in molecules (AIM) theory.
使用可靠的 QM 从头计算方法研究了 O(2)分子在各种材料的酸性铝硅酸盐位模型中的行为。通过不同的基组在有信心的理论水平上计算了孤立 O(2)的三重态-单重态能量间隙，作为参考。考虑了与单重和三重电子态氧相互作用的两种 O(2)排列的铝硅酸盐活性位模型。对未经校正和校正的 BSSE 势能表面进行了几何优化，意识到在这些过程中，对重原子-氢键相互作用进行良好的建模对 BSSE 校正很敏感。进一步在更高的理论水平上评估能量以检验趋势。与计算的三重态氧相比，单线态氧对活性铝硅酸盐位更具吸引力，这表明含有这种分子残基的设计纳米结构具有氧化效率的来源。显然，在几种材料中普遍存在的铝硅酸盐基团可以将 O(2)的三重态-单重态能量间隙降低至少 10 kJ/mol。通过分子中的原子 (AIM) 理论进一步分析了氧与这些位点相互作用的一些巧妙特征。
