Computational Study on Redox-Switchable Second-Order Nonlinear Optical Properties of Totally Inorganic Keggin-Type Polyoxometalate Complexes

	Computational Study on Redox-Switchable Second-Order Nonlinear Optical Properties of Totally Inorganic Keggin-Type Polyoxometalate Complexes
	Liu CG ; Guan XH
刊名	journal of physical chemistry c
	2013
卷号	117 期号:15 页码:7776-7783
关键词	DENSITY-FUNCTIONAL THEORY EFFECTIVE CORE POTENTIALS KETO-ENOL EQUILIBRIUM AB-INITIO MOLECULAR CALCULATIONS LACUNARY POLYOXOMETALATE ELECTRONIC-STRUCTURES MAGNETIC-PROPERTIES DERIVATIVES OXYGEN
ISSN号	1932-7447
通讯作者	liu cg
中文摘要	the electronic structure and second-order nonlinear optical (nlo) property of a series of monoruthenium-substituted keggin-type polyoxometalates (poms) have been studied by using density functional theory (dft) and time-dependent (td)dft calculations. the dft calculation supports that these pom complexes possess donor-pi-conjugated bridge-acceptor (d-pi-a) structure, which the ruthenium atom acts as the role of electron donor and the three vanadium atoms in cap region of keggin-type pom act as the role of electron acceptor. it is well-known that d-pi-a structure, as a simple molecular scheme, has been successfully used in the development of organic nlo materials. however, the totally inorganic molecule having d-pi-a structure is very rare. thereby the second order nlo properties of these pom complexes have been analyzed in this work. according to the calculations, introduction of the electron acceptor leads to a substantial enhancement on the second order nlo response. the calculated beta(hrs)(-2 omega; omega, omega) value of three-vanadium-atom derivative [{pw9v3o39}ru-ii(h2o)](8-) is 34 times as large as that of [{pw11o39}ru-ii(h2o)](5-) according to cam-b3lyp/6-31+g* calculations (lanl2dz basis sets for metal atom) in acetonitrile. because of the redox-active ruthenium center and large second order nlo response, the redox switching of second order nlo responses for the three-vanadium-atom derivative [{pw9v3o39}ru-ii(h2o)](8-) also have been studied. the results show that the ru-ii -> ru-iii oxidation leads to the first hyperpolarizability to decrease remarkably.
收录类别	SCI收录期刊论文
语种	英语
WOS记录号	WOS:000317950300043
公开日期	2014-04-16
内容类型	期刊论文
源URL	[http://ir.ciac.jl.cn/handle/322003/49905]
专题	长春应用化学研究所_长春应用化学研究所知识产出_期刊论文
推荐引用方式 GB/T 7714	Liu CG,Guan XH. Computational Study on Redox-Switchable Second-Order Nonlinear Optical Properties of Totally Inorganic Keggin-Type Polyoxometalate Complexes[J]. journal of physical chemistry c,2013,117(15):7776-7783.
APA	Liu CG,&Guan XH.(2013).Computational Study on Redox-Switchable Second-Order Nonlinear Optical Properties of Totally Inorganic Keggin-Type Polyoxometalate Complexes.journal of physical chemistry c,117(15),7776-7783.
MLA	Liu CG,et al."Computational Study on Redox-Switchable Second-Order Nonlinear Optical Properties of Totally Inorganic Keggin-Type Polyoxometalate Complexes".journal of physical chemistry c 117.15(2013):7776-7783.