水合铝离子单体和二聚体的DFT研究

居学海; 范晓薇; 马海霞; 赵天生

环境化学

水合铝离子单体和二聚体的DFT研究

, , ,

居学海, 范晓薇, 马海霞, 赵天生. 水合铝离子单体和二聚体的DFT研究[J]. 环境化学, 2007, 26(3): 347-351.

引用本文:

居学海, 范晓薇, 马海霞, 赵天生. 水合铝离子单体和二聚体的DFT研究[J]. 环境化学, 2007, 26(3): 347-351.

JU Xue-hai, FAN Xiao-wei, MA Hai-xia, ZHAO Tian-sheng. DFT INVESTIGATIoN oN THE MONOM ERS AND DIMERS OF AQUEOUS ALUMINUM ION[J]. Environmental Chemistry, 2007, 26(3): 347-351.

Citation:

JU Xue-hai, FAN Xiao-wei, MA Hai-xia, ZHAO Tian-sheng. DFT INVESTIGATIoN oN THE MONOM ERS AND DIMERS OF AQUEOUS ALUMINUM ION[J]. Environmental Chemistry, 2007, 26(3): 347-351.

水合铝离子单体和二聚体的DFT研究

1.
南京理工大学化学系, 南京, 210094;
2.
宁夏大学能源化工重点实验室, 银川, 750021
基金项目:
南京理工大学科研启动基金资助课题.

DFT INVESTIGATIoN oN THE MONOM ERS AND DIMERS OF AQUEOUS ALUMINUM ION

1.
Department of Chemistry, Nanjing University of Science and Technology, Nanjing, 210094, China;
2.
Key Laboratory of Energy Resources＆ Cheimcal Engineeirng, Ningxia University, Yinchuan, 750021, China
Fund Project:

摘要: 用DFT方法在B3LYP/6-31G* 水平下,对水合铝离子的单体和二聚体形态进行计算.在单体[Al(H2O)6]3+,[Al(OH)(H2O)5]2+,[Al(OH)2(H2O)4]+和二聚体[Al2(OH)2(H2O)8]4+,[Al2(OH)3(H2O)7]3+,[Al2(OH)4(H2O)6]2+,[Al2(OH)5(H2O)5]+及其异构体中, Al和羟基O之间的键长明显小于Al和H2O中O之间的键长.将H2O代以羟基后,六配位的Al-O八面体骨架发生了较大的畸变.在[Al2(OH)4(H2O)6]2+形态的不同几何异构体中,当2个羟基相互邻近时稳定性较低.羟铝比(OH/Al)增大将有更多的电子流向Al(Ⅲ),同时,单体和二聚体中H2O的氢原子所带正电荷均有所减小.二聚体的羟桥氢原子所带正电荷随OH/Al比的增大而减小.各形态的键强度呈现:Al-O(H2O)＜Al-O(OH)-Al＜Al-O(OH),即Al-Ow＜Al-Ob-h＜Al-Oh.对单体形态,随OH/Al比增大, Al-Ow和Al-Oh键强度均逐渐减小.二聚体形态OH/Al比增大, Al-Ow键强度减小,但Al-Ob-h键强度基本不变, Al-Oh则呈不规则变化.无论是单体还是二聚体,OH/Al比较大形态的HOMO能级与OH/Al比较小形态的LUMO能级相近或前者稍高,前者很容易向后者提供电子.聚合过程主要是在不同形态组分之间进行.
- 水合铝离子 /
- 单体 /
- 二聚体 /
- DFT
Abstract: Quantum chemical calculations for the monomers and dimers of aqueous aluminum ion were performed at the DFT—B3LYP/6—31G*leve1．[Al(H2O)6]3+,[Al(OH)(H2O)5]2+ and [Al(OH)2(H2O)4]+ were claculated FoR the monomers．[Al2(OH)2(H2O)8]4+,[Al2(OH)3(H2O)7]3+,[Al2(OH)4(H2O)6]2+ and [Al2(OH)5(H2O)5]+,as well as their isomers,were calculated for the dimers．The bond length between A1 and hydroxyl O is obviously shorter than that between A1 and water O．The octahedrlaskeleton wiht 6 coordinates is aberrant with water being substituted by hydroxyl groups．Among the isomesr of[A12(OH)4-(H20)6]2+,the stability is lowed by two neighbor hydroxyl groups．With the ratio of OH/A1 increasing,more electrons flow to the A1(Ⅲ),and at the same time,the positive charges on the water hydrogen atoms decrease for both monomers and dimers．The order for the bonds trengths is:Al-O(H20)b-hh．For the monomers,the bond strengths of Al-O and Al-O hdecreaseastheratio of OH／A1 incerases．For the dimesr,the bond strengths of Al-Ow decrease as the ratio of OH／A1 incerases, however the bond strengths of Al-Ob-h hardly vary, and Al-Oh vary irregularly．Th eenergies of HOMOs in isomers with large ratio of OH／A1 are close to or even slightly larger than those of LUMOs with small ratio of OH／A1．and the former could easily donates their electrons to the latter．The polymeriztions take place mainly among different isomers．
- Monomer /
- dimer /
- aqueouslauminum ion /
- DFT

[1]

汤鸿霄,无机高分子絮凝剂的基础研究.环境化学,1990,9(3):1-11
[2] Johasson G,The Crystal Structure of[Al₂(OH)₂(H₂O)₈] (SO₄)₂·2H₂O and[Al₂(OH)₂(H₂O)₈] (SeO₄)₂·2H₂O.Acta Chem.Scand.,1962,16:403-420
[3] 波普尔J A,贝弗里奇D L著,江元生译,分子轨道近似方法.北京:科学出版社,1976,p.115-118
[4] Lee C,Yang W,Parr R G,Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density.Phys.Rev.B,1988,37:785-789
[5] Becke A D,Density-Functional Thermochemistry.III.The Role of Exact Exchange.J.Chem.Phys.,1993,98:5648-5652
[6] Schlegel H B,Optimization of Equilibrium Geometries and Transition Structures,J.Comput.Chem.,1982,3:214-218
[7] Frisch M J,Trucks G W,Schlegel H B et al.,Gaussian 98(Revision A.7),Gaussian,Inc.,Pittsburgh PA,1998
[8] Johansson G,On the Crystal Structure of Some Basic Aluminium Salts.Acta Chem.Scand.,1960,14:771-773
[9] 居学海,赵天生,翟锦库,聚合氯化铝Al₁₃模型化合物的量子化学计算研究.环境化学,2006,25(4):395-399

点击查看大图

计量

文章访问数: 511
HTML全文浏览数: 511
PDF下载数: 325
施引文献: 0

水合铝离子单体和二聚体的DFT研究

1. 南京理工大学化学系, 南京, 210094;
2. 宁夏大学能源化工重点实验室, 银川, 750021

收稿日期: 2006-05-24

基金项目:

南京理工大学科研启动基金资助课题.

关键词:

水合铝离子 /
单体 /
二聚体 /
DFT

摘要: 用DFT方法在B3LYP/6-31G* 水平下,对水合铝离子的单体和二聚体形态进行计算.在单体[Al(H2O)6]3+,[Al(OH)(H2O)5]2+,[Al(OH)2(H2O)4]+和二聚体[Al2(OH)2(H2O)8]4+,[Al2(OH)3(H2O)7]3+,[Al2(OH)4(H2O)6]2+,[Al2(OH)5(H2O)5]+及其异构体中, Al和羟基O之间的键长明显小于Al和H2O中O之间的键长.将H2O代以羟基后,六配位的Al-O八面体骨架发生了较大的畸变.在[Al2(OH)4(H2O)6]2+形态的不同几何异构体中,当2个羟基相互邻近时稳定性较低.羟铝比(OH/Al)增大将有更多的电子流向Al(Ⅲ),同时,单体和二聚体中H2O的氢原子所带正电荷均有所减小.二聚体的羟桥氢原子所带正电荷随OH/Al比的增大而减小.各形态的键强度呈现:Al-O(H2O)＜Al-O(OH)-Al＜Al-O(OH),即Al-Ow＜Al-Ob-h＜Al-Oh.对单体形态,随OH/Al比增大, Al-Ow和Al-Oh键强度均逐渐减小.二聚体形态OH/Al比增大, Al-Ow键强度减小,但Al-Ob-h键强度基本不变, Al-Oh则呈不规则变化.无论是单体还是二聚体,OH/Al比较大形态的HOMO能级与OH/Al比较小形态的LUMO能级相近或前者稍高,前者很容易向后者提供电子.聚合过程主要是在不同形态组分之间进行.

English Abstract

DFT INVESTIGATIoN oN THE MONOM ERS AND DIMERS OF AQUEOUS ALUMINUM ION

1. Department of Chemistry, Nanjing University of Science and Technology, Nanjing, 210094, China;
2. Key Laboratory of Energy Resources＆ Cheimcal Engineeirng, Ningxia University, Yinchuan, 750021, China

Received Date: 2006-05-24

Fund Project:

Keywords:

Monomer /
dimer /
aqueouslauminum ion /
DFT

Abstract: Quantum chemical calculations for the monomers and dimers of aqueous aluminum ion were performed at the DFT—B3LYP/6—31G*leve1．[Al(H2O)6]3+,[Al(OH)(H2O)5]2+ and [Al(OH)2(H2O)4]+ were claculated FoR the monomers．[Al2(OH)2(H2O)8]4+,[Al2(OH)3(H2O)7]3+,[Al2(OH)4(H2O)6]2+ and [Al2(OH)5(H2O)5]+,as well as their isomers,were calculated for the dimers．The bond length between A1 and hydroxyl O is obviously shorter than that between A1 and water O．The octahedrlaskeleton wiht 6 coordinates is aberrant with water being substituted by hydroxyl groups．Among the isomesr of[A12(OH)4-(H20)6]2+,the stability is lowed by two neighbor hydroxyl groups．With the ratio of OH/A1 increasing,more electrons flow to the A1(Ⅲ),and at the same time,the positive charges on the water hydrogen atoms decrease for both monomers and dimers．The order for the bonds trengths is:Al-O(H20)b-hh．For the monomers,the bond strengths of Al-O and Al-O hdecreaseastheratio of OH／A1 incerases．For the dimesr,the bond strengths of Al-Ow decrease as the ratio of OH／A1 incerases, however the bond strengths of Al-Ob-h hardly vary, and Al-Oh vary irregularly．Th eenergies of HOMOs in isomers with large ratio of OH／A1 are close to or even slightly larger than those of LUMOs with small ratio of OH／A1．and the former could easily donates their electrons to the latter．The polymeriztions take place mainly among different isomers．

全文HTML

参考文献 (1)

下载: 全尺寸图片幻灯片

返回文章

用微信扫码二维码

分享至好友和朋友圈

水合铝离子单体和二聚体的DFT研究

DFT INVESTIGATIoN oN THE MONOM ERS AND DIMERS OF AQUEOUS ALUMINUM ION

计量

出版历程

水合铝离子单体和二聚体的DFT研究

English Abstract

DFT INVESTIGATIoN oN THE MONOM ERS AND DIMERS OF AQUEOUS ALUMINUM ION

全文HTML

目录