Bygrave Peter J, Case David H, Day Graeme M
School of Chemistry, University of Southampton, Southampton, United Kingdom.
Faraday Discuss. 2014;170:41-57. doi: 10.1039/c3fd00162h.
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.
评估了计算方法预测决定固态机械化学反应平衡的结构和能量学的能力。使用晶体结构预测方法和晶格能计算，研究了芳香族二硫化物之间两个先前已表征的碱催化复分解反应，该计算将分子电子结构方法与各向异性原子-原子势相结合。我们发现晶格能搜索将六个晶体结构中的三个定位为各自晶体能量景观上的全局最小值。由于密度泛函理论方法在计算分子内能量方面的局限性，导致在模拟相对构象能量时存在问题，因此其余结构的预测不太成功。对于当前方法来说，预测总反应能量具有挑战性，但结果显示出有望作为构建更准确可靠方法的基础。
