从头算的研究金属离子及价态对CO络合吸附性能的影响.pdfVIP

从头算研究金属离子及其价态对CO络合吸附性能的影响 周锦霞，张永春，郭新闻。，宋伟杰，白洪亮 Ck连理工大学精细化工国家重点实验富，辽宁大连116012) 摘要：采用从头计算分子轨道法研究了金属离子及其价态对络合吸附C0性能的影响．计算结果得出络合吸附 论(NBO)对原子电荷、轨道电子分布和轨道能量的分析结果表明：(1)CO的5O填充轨道与M+0“代表 M’的(n-I)d。、(n．1)d，z填充轨道叠加形成d·靠‘反馈键，M+的(n-1)d=2轨道通过CO的5O轨道的“搭桥” 有利于与C0形成较强的络合键． 关．键词：从头计算；CO；络合吸附l金属离子；价态 中图分类号：O“7．3 文献标识码tA AbInitio CationandValence of StateEffects Study n兀一 oltaOI乙ofsC0nonoMetalMetI on兀．Complexation ZHOU Wei．JieandBAI Jin．Xia,ZHANG Xin．Wen‘，SONG Yong．Chun，GUO Hong-Liang ofFine (StateLaboratoryChemical，DalianUniversityofTechnology,Dalianl16012，P．凡China) Key Abstract：Anabinitiomolecularorbitalhasbeen todeterminetheeffectsofthedifferentmetals study performed andtheir valencestates011 ofCOonmetalions．Thecalculatedresults the orderofthe x-eomplexation predictfullowing adsorption tllcdifferentmetals)CO·Cu+CO-Cu2+fortIIcdifferentvalencestates．Theresultsale strength：CO-Cu+CO-Ag+for adetailed ofmetal election andorbital naturalbondorbital explainedby analysis charges,orbitaloccupies energiesusing naRue bondsis transferfromthe O that,electron the 5 orbitalof fNBO)theory：(1)Theof靠-complexation fullyoccupied IISorbital the c0tothevacant ofIW(forCu+，n=4：forAg’。n=5)forms0-donation。electrontransferfromthe orbitalsofhrtothevacant orbitalsofCO d一 fullyoccup