过苯胺黑聚合物的双极化子态
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摘要
利用改进的Ginder-Epstein模型研究聚苯胺黑的双极化子态,给出其键序波幅、芳环扭角、电子能级、理论吸收谱和电荷分布,并与极化子进行对比.结果发现双极化子激发能为3.08eV,晶格驰豫宽度涉及12格点与极化子相当;键交错驰豫深度大约为极化子的2倍,畸变中心芳环扭角高达68.35°大于极化子中心扭角的2倍.两个能隙态几乎简并,吸收谱低能峰为1.6eV.
A bipolaron state in the pernigraniline-base polymer was investigated from an extended Ginder-Epstein model.The ring-angle configuration,bond-length-order waves(BOW),energy levels,absorption spectrum and charge distributions were obtained from the study.Then,they were compared with those in a polaron state.The excitation energy for a bipolaron is 3.08 eV.The depth of the BOW relaxasion of a bipolaron is twice that for a polaron.The maximum angle of the aromatic ring at the relaxasion centre is as large as 68.35°,which is more than twice of that in a polaron.The weak absorption associated the gap states is at 1.6 eV.
A bipolaron state in the pernigraniline-base polymer was investigated from an extended Ginder-Epstein model.The ring-angle configuration,bond-length-order waves(BOW),energy levels,absorption spectrum and charge distributions were obtained from the study.Then,they were compared with those in a polaron state.The excitation energy for a bipolaron is 3.08 eV.The depth of the BOW relaxasion of a bipolaron is twice that for a polaron.The maximum angle of the aromatic ring at the relaxasion centre is as large as 68.35°,which is more than twice of that in a polaron.The weak absorption associated the gap states is at 1.6 eV.
引文
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[3]Friend R.Material science:polymers show they’remetals[J].Nature,2006,441:37.
[4]Su W P,Schrieffer J R,Heeger A J.Solitons inpolyacetylene[J].Phys.Rev.Lett.,1979,42:1698.
[5]Zhu D B,Wang F S.Organic solids[M].Shanghai:Shanghai Scientific and Technical Publishers,1999(in Chinese)[朱道本,王佛松.有机固体[M].上海:上海科学技术出版社,1999]
[6]Kim J,Unterreiner A N,Sachin R,et al.Ultrafastdephasing of photoexcited polarons in primary dopedpolyaniline[J].J.Phys.Chem.B,2002,106:12866.
[7]Genies E M,Lapkowski M.Electrochemical in situEPR evidence of two polaron-bipolaron states inpolyaniline,[J].J.Electro.Chem.InterfacialElectrochem,1987,236:199.
[8]Shaolin M,Jinqing K,Juntao L,et al.Interconver-sion of polarons and bipolarons of polyaniline duringthe electrochemical polymerization of aniline[J].J.Electro.Chem.,1998,466:107.
[9]Krinichnyi V I,Tokareva S V,Roth H K,et al.EPR study of charge transfer in polyaniline highlydoped by p-toluenesulfonic acid[J].Synth.Met.,2006,156:1368.
[10]Ginder M,Epstein A J.Role of ring torsion angle inpolyaniline:electronic structure and defect states[J].Phys.Rev.B,1990,41:10674.
[11]Baranowski D,Büttner H,Voit J.Influence of li-bronic degrees of freedom on electronic properties ofpolyaniline[J].Phys.Rev.B,1992,45:10990.
[12]Liu J,Wu D C.Bond-order soliton associated with aring-torsion soliton in PNB and its IRAV mode[J].Sol.Stat.Commun,1998,107:65.
[13]Johansson,Stafstrm S.Soliton and polarontransport in trans-polyacetylene[J].Phys.Rev.B,2002,65:045207.
[14]Mizes H A,Conwell E M.Stability of polarons inconducting polymers[J].Phys.Rev.Lett.,1993,70:1505.
[15]Baeriswyl D.On the stability of local states in con-jugated polymers[J].Synth.Met.,1991,43:3585.
[16]Johansson,Stafstrm S.Interchain charge trans-port in disorderedπ-conjugated chain systems[J].Phys.Rev.B,2002,66:085208.
[17]Liu J,Wu D C.Combind polarons in a pernigrani-line-base polymer[J].Phys.Lett.A,1998,244:292.
[18]Yang M Z,Liu J.The polaron in pernigraniline-basepolymer under pressure[J].J.At.Mol.Phys.,2011,28:338(in Chinese)[杨茂正,刘杰.过苯胺黑聚合物高压下的极化子态[J].原子与分子物理学报,2011,28:338].
[19]Auslaender O M,Steinberg H,Yacoby A,et al.Spin-charge separation and localization in one dimen-sion[J].Science,2005,308:88.
[20]Liu J,Sun X,Lin D L,et al.Gap states of polaronand associated optical absorption in the quasi-one-di-mensional solid(Pt(en)2)(PtCl2(en)2)(ClO4)4[J].J.Phys.:Condens.Matt.,1992,4:5301.
[21]Murugesan R,Subramanian E.Charge dynamics inconducting polyaniline-metal oxalate composites[J].Bull.Mater.Sci.,2003,26:529.
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