Topological Disorder and Reactivity of Borosilicate Glasses: Quantum Chemical Calculations and 17O and 11B NMR Study
Topological Disorder and Reactivity of Borosilicate Glasses: Quantum Chemical Calculations and 17O and 11B NMR Study
复制标题
硼硅酸盐玻璃的拓扑无序和反应性：量子化学计算和 17O 和 11B NMR 研究
DOI：
10.1021/jp012119f
复制
发表时间：
2001
影响因子：
3.3
通讯作者：
J. Stebbins
中科院分区：
文献类型：
--
作者：
S. Lee;C. Musgrave;Andi Zhao;J. Stebbins
我们提出了17 O和11B NMR和量子化学计算的基础上Hartree-Fock（HF）和密度泛函理论研究的网站连接，化学短程有序度（CSRO），和拓扑短程秩序在二元硼硅酸盐玻璃，它可以作为一个简单的模型系统更复杂的硼硅酸盐和其他共价氧化物玻璃和熔体。我们还计算了这种玻璃中每个氧簇的水解焓。[4]Si−O−[3]B的稳定性是通过在B3 LYP/6-311+G（2d，p）//HF/3- 21 G和B3 LYP/6 - 311 + G（2d，p）理论水平上计算的桥氧团簇（[4] Si −O−[4]Si，[4]Si−O−[3]B和[3]B−O−[3]B）之间的相对能量差以及17 O 3QMAS NMR数据来评估的。当硼的摩尔分数为0.57时，[4]Si−O−[3]B的分数约为37%（±1），表明[3]B和[4]Si的显著的相互分散，其中[4]Si和[3]B的随机分布和完全的相分离导致50%和0%的[4]Si−O−[3]B，相对于[3]B，[4] B的分散程度更高。
We present 17O and 11B NMR and quantum chemical calculations based on Hartree−Fock (HF) and density functional theory to investigate the site connectivity, the degree of chemical short-range order (CSRO), and the topological short-range order in binary borosilicate glasses, which can serve as a simple model system for more complex borosilicates and other covalent oxide glasses and melts. We also calculate the enthalpy of hydrolysis for each oxygen cluster in such glasses. The stability of [4]Si−O−[3]B was evaluated from the relative energy differences among the bridging oxygen clusters ([4]Si−O−[4]Si, [4]Si−O−[3]B, and [3]B−O−[3]B) calculated at the B3LYP/6-311+G(2d,p)//HF/3-21G and B3LYP/6-311+G(2d,p) levels of theory as well as data from 17O 3QMAS NMR. The fraction of [4]Si−O−[3]B at a boron mole fraction of 0.57 is about 37% (±1), suggesting a significant inter-dispersion of [3]B and [4]Si, where a random distribution of [4]Si and [3]B and complete phase separation lead to 50 and 0% of [4]Si−O−[3]B, re...