关于乳酸在氧化镁团簇表面反应的理论研究。
Theoretical investigation of surface reactions of lactic acid on MgO clusters.
机构信息
Department of Chemistry, Kansas State University, Manhattan, Kansas 66506, United States.
出版信息
J Phys Chem A. 2013 Jan 31;117(4):765-70. doi: 10.1021/jp309801b. Epub 2013 Jan 15.
Interaction of lactic acid with various sizes of magnesium oxide clusters (MgO)(x) (x = 2, 4, 6, 8, 9, 12, 15, 16, 18) is investigated. Density functional theory with the PBE functional and a polarized double-ζ basis set is employed to optimize the structures. For MgO dimer, optimizations are also performed at the PBE/DZP, PBE/TZP, and MP2/TZV(d,p) levels of theory, and single-point CCSD(T)/TZV(d,p) calculations are computed at the PBE/TZP optimized geometries. CCSD(T)/TZV(d,p) calculations show that the PBE/DZP results are off by no more than 5 kcal/mol. Dissociative adsorption of a proton bound to oxygen is possible for the carboxylic acid group, the hydroxyl group, and for a simultaneous interaction of the carboxylic acid and hydroxyl groups. Associative adsorption of various functional groups is also possible, although these represent higher energy structures. All of the adsorptions are calculated to be exothermic. Dissociative adsorption of the carboxylic acid group of lactic acid at the lowest coordinated magnesium sites is determined to be the lowest energy structure. Adsorption energies are found to decrease in magnitude as the size of MgO increases. The geometry of the magnesium oxide cluster changes to a nanorod-like structure when lactic acid interacts with higher coordinated magnesium atoms in double layer systems, but remains simple cubic when a third layer is added. The coordination environment rather than the size of the MgO cluster appears to dominate the adsorption energy when the size becomes larger than (MgO)(12).
研究了乳酸与不同尺寸的氧化镁团簇(MgO)(x)(x=2、4、6、8、9、12、15、16、18)的相互作用。采用 PBE 泛函和极化双 ζ 基组的密度泛函理论来优化结构。对于 MgO 二聚体,还在 PBE/DZP、PBE/TZP 和 MP2/TZV(d,p)理论水平上进行了优化,并且在 PBE/TZP 优化的几何结构上进行了单点 CCSD(T)/TZV(d,p)计算。CCSD(T)/TZV(d,p)计算表明,PBE/DZP 结果的误差不超过 5 kcal/mol。对于羧酸基团、羟基和羧酸基团与羟基的同时相互作用,质子与氧的缔合吸附是可能的。各种官能团的缔合吸附也是可能的,尽管这些代表了更高的能量结构。所有的吸附都是放热的。乳酸的羧酸基团在配位最低的镁位上的解离吸附被确定为最低能量结构。随着氧化镁尺寸的增加,吸附能的大小呈下降趋势。当乳酸与双层系统中配位较高的镁原子相互作用时,氧化镁团簇的几何形状变为纳米棒状结构,但当添加第三层时,仍保持简单立方结构。当尺寸大于(MgO)(12)时,似乎是配位环境而不是 MgO 团簇的大小主导了吸附能。