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Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-alpha,omega-diphenylpolyenes and alpha,omega-diphenylpolyynes
Ma, Xiaonan; Yan, Linyin; Wang, Xuefei; Guo, Qianjin1; Xia, Andong
Source PublicationPHYSICAL CHEMISTRY CHEMICAL PHYSICS
2011
DOI10.1039/c1cp21036j
Volume13Issue:38Pages:17273-17283
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS Research AreaChemistry ; Physics
WOS KeywordEFFECTIVE 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
AbstractThe 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.
Language英语
WOS IDWOS:000295128000042
Citation statistics
Cited Times:15[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/142331
Collection中国科学院大连化学物理研究所
Affiliation1.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
GB/T 7714
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.
APA Ma, Xiaonan,Yan, Linyin,Wang, Xuefei,Guo, Qianjin,&Xia, Andong.(2011).Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-alpha,omega-diphenylpolyenes and alpha,omega-diphenylpolyynes.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,13(38),17273-17283.
MLA Ma, Xiaonan,et al."Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-alpha,omega-diphenylpolyenes and alpha,omega-diphenylpolyynes".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 13.38(2011):17273-17283.
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