苯胺及掺杂态苯胺低聚物结构的密度泛函理论研究
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摘要
采用基于密度泛函理论的计算方法,研究了苯胺低聚物及盐酸、对甲苯磺酸掺杂苯胺低聚物的几何结构和电子结构.结果表明,质子酸掺杂使苯胺低聚物分子链上醌环中C-C单、双键交替的性质被削弱,同时链间C=N键长明显增大.掺杂位上链间C-N-C键角增大,相邻环间的扭转角减小,分子链的共面性有所改善.与盐酸掺杂对比,对甲苯磺酸掺杂更利于电子从环内向链间转移,理论上可更好地改善聚苯胺材料的导电性能.
A comprehensive study about the geometric structure and electronic structure of aniline oligomer and hydrochloric acid,p- toluene sulfonic acid doped oligomer has been developed using theoretical calculation method based on density functional theory. The results show that the property of C- C bond length of quinone ring in Oligoaniline molecular chains alternating in the way of single and double bond is obviously weakened by doped proton- acid,and the bond length of C = N between chains is significantly increased. The bond angle of C- N- C on doping site is increased and the torsion angle between adjacent rings is reduced. Coplanar of the molecular is improved by acid doping. Compared with HCl,doping with p- toluene sulfonic acid is more conducive to transfer electron from the aromatic rings to the molecular chains,so doping with organic acid can better improve the conductivity of Polyaniline material theoretically.
A comprehensive study about the geometric structure and electronic structure of aniline oligomer and hydrochloric acid,p- toluene sulfonic acid doped oligomer has been developed using theoretical calculation method based on density functional theory. The results show that the property of C- C bond length of quinone ring in Oligoaniline molecular chains alternating in the way of single and double bond is obviously weakened by doped proton- acid,and the bond length of C = N between chains is significantly increased. The bond angle of C- N- C on doping site is increased and the torsion angle between adjacent rings is reduced. Coplanar of the molecular is improved by acid doping. Compared with HCl,doping with p- toluene sulfonic acid is more conducive to transfer electron from the aromatic rings to the molecular chains,so doping with organic acid can better improve the conductivity of Polyaniline material theoretically.
引文
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[2]Masanobu M,Takuya A.Properties and stability of polyaniline nanofiber ammonia sensors fabricated by novel on-substrate method[J].Sensors and Actuators B,2011,160:999.
[3]Tai H L,Jiang Y D,Xie G Z,et al.Preparation,characterization and comparative NH3-sensing characteristic studies of PANI/inorganic Oxides nanocomposite thin films[J].Journal of Materials Sciences and Technology,2010,7:605.
[4]Liu H Y,Wang S B,Zhu Y,et al.Hydrothermal synthesis of polyaniline-iron oxide nano-composite materials[J].Chemical Journal of Chinese Universities,2013,34(5):1303(in Chinese)[刘红缨,王双宝,朱英,等.水热法制备聚苯胺及其铁氧化物纳米复合材料[J].高等学校化学学报,2013,34(5):1303]
[5]Lim S L,Tana K L.A comparative ab initio and DFT study of neutral aniline oligomers[J].Journal of Chemical Physics,2000,122(23):10648.
[6]Cavazzoni C,Colle R,Farchioni R,et al.Car-Parrinello molecular dynamics study of electronic and structural properties of neutral polyanilines[J].Physical Review B,2002,66:165110.
[7]Foreman J P,Monkman A P.Theoretical investigations into the structural and electronic influences on the hydrogen bonding in doped polyaniline[J].The Journal of Physical Chemistry A,2003,107:7604.
[8]Varela A,lvarez A,Sordo J,et al.Doping of polyaniline by acid-base chemistry:Density functional calculations with periodic boundary conditions[J].The Journal of the American Chemical Society,2005,127:11318.
[9]Casanovas J,Aleman C.Comparative theoretical study of heterocyclic conducting oligomers neutral and oxidized forms[J].The Journal of Physical Chemistry C,2007,111:4823.
[10]Zhekova H,Tadjer A,Ivanova A,et al.Theoretical study of the structure and electronic spectra of fully protonated emeraldine Oligomers[J].International Journal of Quantum Chemistry,2007,107:1688.
[11]Colle R,Parruccini P,Benassi A,et al.Optical properties of emeraldine salt polymers from ab initio calculations:Comparison with recent experimental data.[J].The Journal of Physical Chemistry B,2007,111:2800.
[12]Cavazzoni C,Colle R,Farchioni R,et al.Acidification of three-dimensional emeraldine polymers:Search for minimum energy paths from base to salt[J].Journal of Chemical Physics,2008,128:234903.
[13]Aleman C,Ferreira C A,Torras J,et al.On the molecular properties of polyaniline:A comprehensive theoretical study[J].Polymer,2008,49:5169.
[14]Yang G,Hou W,Feng X O,et al.Electronic structure of oligoaniline doped by inorganic and organic acids[J].International Journal of Quantum Chemistry,2008,108:1155.
[15]Casanovas J,Canales M,Ferreira C A,et al.A first principle analysis of the structure of oligoanilines doped with alkylsulfonic acids[J].The Journal of Physical Chemistry A,2009,113:8795.
[16]Zhang H F,Zhang S D,Kong X H.Vibrational spectrum of C6H5NH2in S1state and ab initio calculations[J].Journal of Atomic and Molecular Physics(原子与分子物理学报),2010,27(4):643.
[17]Paterno L G,Mattoso L H C.Influence of different dopants on the ddsorption,morphology,and properties of self-assembled films of Poly(o-ethoxyaniline)[J].Journal of Applied Polymer Science,2002,83:1309.
[18]Mac Diarmid A G,Chiang J C,Richter A F,et al.Polyanilne:a new concept in conducting polymers[J].Synthetic Metals,1987,18(1-3):285.
[19]Mac Diarmid A G,Epstein A J.Secondary doping in polyanilne[J].Synthetic Metals,1995,69:22.
[20]Accelrys Incorporation,Material Studio,Accelrys Inc:San Diego,CA.
[21]Zhang F L,Wu X F.Density functional theory study of3-octylthien-2,5-ylenediethynylene-co-benzo[c]-1’2’5’-thiadiazo-3,6-ylenedi adsorption on Ti O2(100)Surface[J].Journal of Atomic and Molecular Physics,2012,29(5):927(in Chinese)[张福兰,吴兴发.4,7-二(2-噻吩基)苯并噻二唑-3-辛基噻吩二炔在Ti O2(100)表面吸附的密度泛函理论研究[J].原子与分子物理学报,2012,29(5):927]
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