文献类型：期刊文献

英文题名：Density functional theory study on the interaction between metalloporphyrins and NH3

作者：Cao, Zhenfeng[1,2];Chen, Qibin[1,2];Lu, Yunxiang[1,2];Liu, Honglai[1,2];Hu, Ying[1,2]

机构：[1]E China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Dept Chem, Shanghai 200237, Peoples R China

年份：2013

卷号：113

期号：8

起止页码：1137

外文期刊名：INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

收录：;EI(收录号：20131116122056);WOS:【SCI-EXPANDED(收录号:WOS:000315957500010)】；

基金：Contract grant sponsor: National Natural Science Foundation of China; contract grant numbers: 20806025, 21103047, and 21136004.Contract grant sponsor: The 111 Project of China; contract grant number: B08021.Contract grant sponsor: The Fundamental Research Funds for the Central Universities of China.

语种：英文

外文关键词：DFT; linear correlation; Fukui functions; binding strength

摘要：The binding behaviors of eight bivalent metalloporphyrins (MPs) (MZn, Mg, Cu, Mn, Fe, Co, Ni, and Cd) with NH3 were investigated by density functional theory. For both MPs and corresponding complexes MPs-NH3, good linear correlations are found between the partial charge on metal M and that on atom N (nitrogen of porphyrin) as well as the MN bond length. Natural population and frontier orbital analysis demonstrate that charge transfer in CoP-NH3 is much easier and greater. As a consequence of the charge transfer and the hybridization of molecular energy levels, striking disparities of electronic properties of MPs-NH3 are observed. Particularly, a modest linear relationship is obtained between the magnitude of charge transfer and the binding energy. The much greater Fukui functions of CoP, together with its larger binding strength, suggest that CoP is more favorable to the interaction with NH3, which might be a promising sensing material to response NH3. (c) 2013 Wiley Periodicals, Inc.