CAJ | 학술논문

综述了本研究小组利用量子化学簇模型方法研究金属氧化物表面化学吸附和反应的工作.提出了选簇的三个原则,即电中性原则、化学配比原则和配位原则.发现在符合前两个原则的基础上,一个具有最饱和配位、或最少悬空键的簇往往是一个用于化学吸附研究的好的簇模型.与此同时,探讨了如何恰当地考虑大块固体本底的长程影响,提出了用球电荷模拟簇模型的环境、环境与簇体进行电荷自洽的SPC簇模型方法.利用该模型研究了一系列具有催化背景的重要体系,包括H2/ZnO、O/MgO、NO/MgO、N2O/MgO、N2O/Li/MgO、CO/MgO、CO/NiO等.
종술료본연구소조이용양자화학족모형방법연구금속양화물표면화학흡부화반응적공작.제출료선족적삼개원칙,즉전중성원칙、화학배비원칙화배위원칙.발현재부합전량개원칙적기출상,일개구유최포화배위、혹최소현공건적족왕왕시일개용우화학흡부연구적호적족모형.여차동시,탐토료여하흡당지고필대괴고체본저적장정영향,제출료용구전하모의족모형적배경、배경여족체진행전하자흡적SPC족모형방법.이용해모형연구료일계렬구유최화배경적중요체계,포괄H2/ZnO、O/MgO、NO/MgO、N2O/MgO、N2O/Li/MgO、CO/MgO、CO/NiO등.
The research on the cluster modeling of chemisorption and reactions on metal oxide surfaces in our group has been reviewed. Three principles, namely, neutrality principle, stoichiometrical principle and coordination principle were proposed for building up cluster models of metal oxides. Good correlation between the topologic parameters Nc (βc), Na (βa) and Nd (βd) with the stability of clusters has been shown. The problem of how the ways of embedding affect the calculated electronic properties of the substrate clusters and the adsorption properties has been investigated. Based on these, we proposed an SPC model, which is a stoichiometric cutout cluster embedded in a spherically expanded point charge surrounding with charges being self-consistently determined. We have successfully applied the SPC model to a variety of important systems, including H2/ZnO, O/MgO, NO/MgO,N2O / MgO, N2O / Li / MgO, CO / MgO and CO / NiO.