Is the equilibrium composition of mechanochemical reactions predictable using computational chemistry?
Is the equilibrium composition of mechanochemical reactions predictable using computational chemistry?
复制标题
DOI：
10.1039/c3fd00162h
复制
发表时间：
2014-01-01
影响因子：
3.4
通讯作者：
Day, Graeme M.
中科院分区：
文献类型：
--
作者：
Bygrave, Peter J.;Case, David H.;Day, Graeme M.
计算方法的能力来预测的结构和能量，确定固态机械化学反应的平衡进行了评估。两个先前表征的芳族二硫化物之间的碱催化复分解反应进行了研究，使用晶体结构预测方法和晶格能计算，联合收割机分子电子结构方法与各向异性原子-原子势。我们发现，晶格能量搜索定位三个六个晶体结构的全球最小值在各自的晶体能量景观。其余的结构是不太成功的预测，由于相对构象能量建模的问题，由于计算分子内能量的密度泛函理论方法的局限性。整体反应能量的预测证明了当前方法的挑战性，但结果显示出作为建立更准确和可靠方法的基础的希望。
The ability of computational methods to predict the structures and energetics that determine the equilibrium of solid state mechanochemical reactions has been assessed. Two previously characterised base-catalysed metathesis reactions between aromatic disulfides are studied using crystal structure prediction methods and lattice energy calculations that combine molecular electronic structure methods with anisotropic atom-atom potentials. We find that lattice energy searches locate three of the six crystal structures as global minima on their respective crystal energy landscapes. The remaining structures are less successfully predicted, due to problems modelling relative conformational energies due to limitations of the density functional theory method for calculating intramolecular energies. Prediction of the overall reaction energies proves challenging for current methods, but the results show promise as a base on which to build more accurate and reliable approaches.