Dolgonos Grygoriy, Aradi Bálint, Moreira Ney H, Frauenheim Thomas
Bremen Center for Computational Materials Science, University of Bremen, Am Fallturm 1, 28359 Bremen, Germany.
J Chem Theory Comput. 2010 Jan 12;6(1):266-78. doi: 10.1021/ct900422c. Epub 2009 Dec 18.
A new self-consistent-charge density-functional tight-binding (SCC-DFTB) set of parameters for Ti-X pairs of elements (X = Ti, H, C, N, O, S) has been developed. The performance of this set has been tested with respect to TiO2 bulk phases and small molecular systems. It has been found that the band structures, geometric parameters, and cohesive energies of rutile and anatase polymorphs are in good agreement with the reference DFT data and with experiment. Low-index rutile and anatase surfaces were also tested. For molecular systems, binding and atomization energies close to their DFT analogues have been achieved. Large errors, however, have been found for systems in high-spin states and/or having multireference character of their wave functions. The correct performance of SCC-DFTB for surface reactions has been demonstrated via the water splitting on anatase (001) surface. The current SCC-DFTB set is a suitable tool for future in-depth investigation of chemical processes occurring on the surfaces of TiO2 polymorphs as well as for other processes of physicochemical interest.
已经开发出了一套新的用于钛与其他元素（X = Ti、H、C、N、O、S）对的自洽电荷密度泛函紧束缚（SCC-DFTB）参数集。该参数集的性能已针对TiO₂体相和小分子体系进行了测试。结果发现，金红石型和锐钛矿型多晶型物的能带结构、几何参数和内聚能与参考密度泛函理论（DFT）数据以及实验结果吻合良好。还对低指数金红石型和锐钛矿型表面进行了测试。对于分子体系，已获得接近其DFT类似物的结合能和原子化能。然而，对于高自旋态体系和/或具有多参考波函数特征的体系，发现了较大误差。通过锐钛矿（001）表面上的水分解，证明了SCC-DFTB在表面反应中的正确性能。当前的SCC-DFTB参数集是未来深入研究TiO₂多晶型物表面发生的化学过程以及其他具有物理化学意义的过程的合适工具。
