SYSTEMATIC ABINITIO ECP (EFFECTIVE CORE POTENTIAL) STUDIES ON THE FE(H20)+ COMPLEX AND THE IONIZATION AND EXCITATION-ENERGIES OF FE AND FE+

被引:12
作者
FIEDLER, A
HRUSAK, J
SCHWARZ, H
机构
来源
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS | 1992年 / 175卷
关键词
EFFECTIVE CORE POTENTIAL CALCULATIONS; TRANSITION METAL IONS; ION-WATER COMPLEX;
D O I
10.1524/zpch.1992.175.Part_1.015
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Several basis sets are tested by employing ab initio effective core potential calculations, in order to evaluate the excitation energies (DELTAE) of the transitions 5D --> 5F and 5D --> 3F for the iron atom and 6D --> 4F for the Fe+ cation, respectively. In addition, the ionization energies (IE) for the process Fe(5D) --> Fe+ (6D) are calculated. Furthermore, the geometry and the bond dissociation energy of the Fe(H2O)+ complex are computed and compared with experimental as well as other theoretical data. It is demonstrated that for a given theoretical level the basis set used is of minor importance for the determination of DELTAE. However, the inclusion of correlation effects give satisfactory if not excellent agreement with the experimental data. Similarly, the bond dissociation energy of the process Fe(H2O)+ --> Fe+(6D) + H2O is very well reproduced at the MP2 and CISD(+D) level of theory for all the basis sets used. In distinct contrast, even at the highest level of theory the ionization energies are always underestimated up to 11 %.
引用
收藏
页码:15 / 23
页数:9
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