Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile

CORC > 上海应用物理研究所 > 中国科学院上海应用物理研究所 > 中科院上海应用物理研究所2004-2010年

	Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile
	Zhu, G（朱光来） ; Wu, G(吴国忠） ; Sha, M（沙茂林） ; Long, D（龙德武） ; Yao, S（姚思德）
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2008
卷号	112 期号:14 页码:3079
ISSN号	1089-5639
通讯作者	Wu, G (reprint author), Chinese Acad Sci, Shanghai Inst Appl Phys, POB 800204, Shanghai 201800, Peoples R China
英文摘要	The transient absorption spectra and photoinduced electron-transfer process of duroquinone (DQ) in mixed binary solutions of ionic liquid (IL) [bmim][PF6] and acetonitrile (MeCN) have been investigated by laser photolysis at an excitation wavelength of 355 nm. A spectral blue shift of (3)DQ* was observed in the IL/MeCN mixtures compared to MeCN. At lower V-IL(volume fraction of IL), the interaction between DQ and the solvent is dominant, and the decay rate constant (k(obs)) of (3)DQ* increases steadily with the increasing of V-IL; to the contrary, at higher V-IL, the network structures due to the hydrogen bond and viscosity are dominant, and the decay rate constant decreases obviously with increasing V-IL. A critical point (turnover) was observed at V-IL = similar to 0.30. The dependence of the observed growth rate (k(gr)) of the photoinduced electron-transfer (PET) products on V-IL is complex and shows a special change; k(gr) first decreases with increasing V-IL, then increases, and finally decreases slowly with further increasing of V-IL. It is speculated that the PET process in the mixture can be affected by factors including the local structure and the reorganization energy of the solvent and salt and cage effects. The change of local structure of [bmim][PF6]/MeCN is supported by following the steady-state fluorescence behavior of the mixture, in combination with the molecular dynamics simulation of the thermodynamic property. The results revealed that the degree of self-aggregation of monomeric cations (bmim(+)) to associated forms increases with increasing V-IL. This is in good agreement with the laser photolysis results for the same solutions.
学科主题	Physics
收录类别	SCI
语种	英语
WOS记录号	WOS:000254659700012
公开日期	2012-04-18
内容类型	期刊论文
源URL	[http://ir.sinap.ac.cn/handle/331007/7710]
专题	上海应用物理研究所_中科院上海应用物理研究所2004-2010年
推荐引用方式 GB/T 7714	Zhu, G,Wu, G,Sha, M,et al. Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2008,112(14):3079.
APA	Zhu, G,Wu, G,Sha, M,Long, D,&Yao, S.(2008).Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile.JOURNAL OF PHYSICAL CHEMISTRY A,112(14),3079.
MLA	Zhu, G,et al."Effects of ionic liquid [bmim][PF6] on absorption spectra and reaction kinetics of the duroquinone triplet state in acetonitrile".JOURNAL OF PHYSICAL CHEMISTRY A 112.14(2008):3079.