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题名: Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-alpha,omega-diphenylpolyenes and alpha,omega-diphenylpolyynes
作者: Ma, Xiaonan;  Yan, Linyin;  Wang, Xuefei;  Guo, Qianjin1;  Xia, Andong
刊名: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
发表日期: 2011
DOI: 10.1039/c1cp21036j
卷: 13, 期:38, 页:17273-17283
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: The absorption spectra and intramolecular charge transfer (CT) properties of terminal donor/acceptor-substituted all-trans-alpha,omega-diphenylpolyenes (DPE) and alpha,omega-diphenylpolyynes (DPY) molecules with different conjugated bridge length and substitution modes were investigated by using quantum chemical calculations. We calculated the ground state structures and energy of two series of terminal donor/acceptor DPE and DPY by DFT method. The dependence of conjugation length and substitution modes of the electronic absorption spectra was obtained by TDDFT calculation. The hybrid-GGA XC-functional PBE0 employed in this work was selected from several functionals by comparing the calculated electronic spectral data with experimental value. The CIS-based generalized Mulliken-Hush (GMH) approach was further used to calculate coupling values H(AD) of the CT process. The calculation shows that both the HOMO-LUMO energy gaps and average bond length alternations between unsaturated multiple (C C and C = C) and saturated single bonds (C-C) decrease regularly with the extension of conjugation. The effective conjugated length (ECL) of DPE and DPY with the same order MM > MP/PM > PP is found together with the regular red shift of the electronic absorption spectra with the extension of conjugation, resulting from the different pi-electron delocalization and conjugation efficiency. The GMH analysis further suggests that the CT process in both DPE and DPY is predominated by the through-bond mechanism. The remarkable difference of the conjugated length dependence of squared CT coupling between substituted DPE and DPY is the result of the energetic matching degree of the frontier molecular orbitals between donor/acceptor and the conjugated bridge.
关键词[WOS]: EFFECTIVE CONJUGATION LENGTH ;  DONOR-ACCEPTOR SUBSTITUTION ;  EXCITATION-ENERGY TRANSFER ;  GENERALIZED MULLIKEN-HUSH ;  DENSITY-FUNCTIONAL THEORY ;  PHOTOINDUCED ELECTRON-TRANSFER ;  COUPLING MATRIX-ELEMENTS ;  TRANSFER EXCITED-STATES ;  LONG-RANGE ELECTRON ;  SPECTROSCOPIC PROPERTIES
语种: 英语
WOS记录号: WOS:000295128000042
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142331
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing 100190, Peoples R China
2.Chinese Acad Sci, Inst Chem, BNLMS, Beijing 100190, Peoples R China

Recommended Citation:
Ma, Xiaonan,Yan, Linyin,Wang, Xuefei,et al. Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-alpha,omega-diphenylpolyenes and alpha,omega-diphenylpolyynes[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2011,13(38):17273-17283.
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