The effect of ligands on the first hyperpolarizabilities of rich d electron molecular system: iridium clusters, a TDDFT study
Authors: Li, Fujun1; Sa, Rongjian1; Wu, Kechen1
Source: Molecular Physics, Volume 106, Numbers 21-23, November 2008 , pp. 2537-2544(8)
Publisher: Taylor and Francis Ltd
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Abstract:
A systematically varied series of tetrahedral iridium clusters have been studied using a TDDFT method focusing on their electronic and nonlinear optical properties. The clusters W2Ir2(CO)10(η5-C5H4Me)2 (1), WIr3(μ-dppe)(CO)9(η5-C5H4Me (2), W2Ir2(μ-L)(CO)8(η5-C5H4Me)2(L = dppe 3, dppf 4), Ir4(μ-L)(CO)10(L = dppm 5, dppe 6, Ph2P(CH2)3PPh2 7, Ph2P(CH2)4PPh2 8, (Ph2P)2CHMe 9), Ir4(CO)10(phen)(phen = 1,10-phenanthroline) (10) exhibit the first static hyperpolarizabilities of medium magnitude (βtot ∼ 10 × 10-30esu). The origination of β is discussed in terms of the electronic structure calculation and the expanded orbital decomposition scheme. The result suggests the origination of β for all the clusters are mainly d-d electron transitions intra metal skeleton, and d-π* electron transitions from metals to carbonyls. For cluster 5, which contains the ferrocenyl group, the main origination of β involves charge transfer from d orbitals of ferrocene to d orbirals of Ir and W.Keywords: TDDFT; UV-Vis spectrum; transition metal; nonlinear optical
Document Type: Research article
DOI: 10.1080/00268970802585084
Affiliations: 1: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, China
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