Pd_n-CO(n=1～7)簇模型的从头算研究  

Ab Initio Studies on Pd_n-CO (n = 1～7) Cluster Models

作　　者：徐昕[1] 王南钦[1] 吕鑫[1] 张乾二[1] 

机构地区：[1]厦门大学化学系固体表面物理化学国家重点实验室,厦门361005

出　　处：《化学学报》1995年第7期670-676,共7页Acta Chimica Sinica

基　　金：国家自然科学基金重大项目;国家教委博士点基金资助课题

摘　　要：本文采用带相对论校正赝势的金属态原子基组，对Ｐｄｎ－ＣＯ（ｎ＝１－７）簇模型进行了从头算研究，通过比较依据最低自旋态原则和金属态原则的计算结果，指出了两种原则的优缺点，总的计算结果表明，依据金属态原则，其结果可以更好地符合ＣＯ／Ｐｄ吸附体系的实验数据，并认为ＣＯ／Ｐｄ吸附过程的成键作用主要是ＣＯ（５σ）→Ｐｄ（５ｓｐ）与Ｐｄ（ｓｐ）→ＣＯ（２π）的σ／π授受作用。Ab initio calculations with relativistic effective core potential have been performed to study Pdn-CO clusters with n ranging from 1 to 7. Attention has been focused on the comparison between the results of ' Lowest Spin State Principle' and those of ' Metallic State Principle' . Better agreement between metallic Pdn-CO clusters and CO / Pd chemisorption systems demonstrates that the 'Metallic State Principle' overweighs the 'Lowest Spin State Principle'. According to the 'Metallic State Principle' the bonding mechanism in CO / Pd adsorption system can be described as CO(5σ)→Pd(5sp) σ donation and Pd(5sp) →CO(2π*) π backdonation.

关 键 词：簇模型 钯 羰基 从头算 自旋态原则 量子化学 

分 类 号：O614.823[理学—无机化学] O641.121[理学—化学]