VU University Amsterdam, Faculty of Earth and Life Sciences, 1081HV, Amsterdam, The Netherlands.
Phys Chem Chem Phys. 2011 Apr 28;13(16):7371-7. doi: 10.1039/c0cp01637c. Epub 2011 Mar 18.
We examine the structure of the hydrated Ti(IV) complex under both ambient and supercritical conditions using first-principles molecular dynamics. We find that an unanticipated fivefold coordination of Ti(IV) is favoured under ambient conditions, with rapid interconversions between square pyramidal and trigonal bipyramidal structures. At supercritical conditions the Ti coordination increases from five to six, adopting both octahedral and trigonal prismatic geometries. At 1000 K, the magnitude of the increase in the Ti to oxygen coordination number with increasing water density is similar to that of Li-O under comparable conditions. We present a detailed picture of the bonding in the hydrated Ti(IV) complex under both ambient and supercritical conditions.
我们使用第一性原理分子动力学研究了常压和超临界条件下水合 Ti(IV) 配合物的结构。我们发现，Ti(IV)在常压下优先形成意想不到的五配位，其结构在四方锥和三角双锥之间快速转换。在超临界条件下，Ti 的配位数从五增加到六，同时具有八面体和三角棱柱体两种构型。在 1000 K 时，随着水密度的增加，Ti 与氧的配位数增加的幅度与 Li-O 在类似条件下的增加幅度相似。我们给出了在常压和超临界条件下水合 Ti(IV)配合物的详细成键情况。
