Theoretical study of the electronic structure and conduction properties of polyfluoroacetylenes and their copolymers

Abstract Results of ab initio band structure calculations of fluorinated polyacetylenes, namely polymonofluoroacetylene (PMFA) and polydifluoroacetylene (PDFA), in both cis and trans configurations are presented. Comparison of the important electronic properties, such as band gap, ionization potential and electron affinity, of the more stable trans forms of PMFA and PDFA with those of trans -polyacetylene (PA) indicates that both PMFA and PDFA are expected to be better intinsic semiconductors than PA, and that they also have better prospects for forming highly conducting n-doped materials. The problem of the copolymerization of fluoroacetylenes with acetylene is also examined, and the electronic density of states (DOS) has been determined for the various periodic and random copolymers. The conduction properties of these copolymers are compared and discussed.

[1]  A. Bakhshi,et al.  Quantum mechanical treatment of biopolymers as solids: Possible implications for carcinogenesis , 1986 .

[2]  S. Suhai,et al.  Quasiparticle energy-band structures in semiconducting polymers: Correlation effects on the band gap in polyacetylene , 1983 .

[3]  M. Aldissi.  Review of the synthesis of polyacetylene and its stabilization to ambient atmosphere , 1984 .

[4]  A. Heeger,et al.  The electronic and electrochemical properties of poly(isothianaphthene) , 1985 .

[5]  G. G. Miller,et al.  Solid-state synthesis of highly conducting polyphenylene from crystalline oligomers , 1980 .

[6]  J. Delhalle,et al.  Electronic structure of polyethylene: Theory and ESCA measurements , 1974 .

[7]  F. E. Karasz,et al.  Electrically conducting acetylene-methylacetylene copolymers. Synthesis and properties , 1981 .

[8]  K. Fukui,et al.  Electronic properties of pure and doped polyacetylenes , 1979 .

[9]  A. Heeger,et al.  Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH)x , 1977 .

[10]  Jean-Marie André,et al.  L'Étude Théorique des Systèmes Périodiques. II. La Méthode LCAO ? SCF ? CO , 1967 .

[11]  A. Bakhshi,et al.  Ab initio study of the electronic structures and conduction properties of nitrogen containing analogues of polyacetylene , 1986 .

[12]  K. Fukui,et al.  The electronic structures of cis-polyacetylene , 1979 .

[13]  G. Tourillon,et al.  New electrochemically generated organic conducting polymers , 1982 .

[14]  K. Yoshino,et al.  Electrical Properties of Conducting Polymer, Poly-Thiophene, Prepared by Electrochemical Polymerization , 1982 .

[15]  K. Yoshino,et al.  Characteristics of Electro-Optic Device Using Conducting Polymers, Polythiophene and Polypyrrole Films , 1983 .

[16]  C. K. Chiang,et al.  Synthesis of highly conducting films of derivatives of polyacetylene, (CH)x , 1978 .

[17]  A. Bakhshi,et al.  On the electronic properties of polyisothianaphthene , 1987 .

[18]  Paul J. Nigrey,et al.  Organic batteries: reversible n- and p- type electrochemical doping of polyacetylene, (CH)x , 1981 .

[19]  M. Aldissi.  Polyacetylene block copolymers , 1986 .

[20]  C. K. Chiang,et al.  Electrical Conductivity in Doped Polyacetylene. , 1977 .

[21]  P. Dean.  The Vibrational Properties of Disordered Systems: Numerical Studies , 1972 .

[22]  Masamichi Kobayashi,et al.  Structure and ferroelectric phase transition of vinylidene fluoride-trifluoroethylene copolymers: 2. VDF 55% copolymer , 1984 .

[23]  A. Bakhshi,et al.  On the electronic structure and conduction properties of aperiodic DNA and proteins. IV. Electronic structure of aperiodic proteins , 1986 .

[24]  Jean-Marie André,et al.  L'Étude Théorique des Systèmes Périodiques. II. La MéthodeLCAOSCFCO: LA MÉTHODELCAOSCFCO-II , 1967 .

[25]  K. Yoshino,et al.  Proposal of Electro-Optical Switching and Memory Devices Utilizing Doping and Undoping Processes of Conducting Polymers , 1983 .

[26]  J. Chien,et al.  Electronic transport and paramagnetic properties of acetylene–carbon monoxide copolymers , 1985 .

[27]  R. Baughman,et al.  Ab initio effective Hamiltonian study of the electronic properties of conjugated polymers , 1982 .

[28]  R. L. Elsenbaumer,et al.  Structural basis for semiconducting and metallic polymer dopant systems , 1982 .

[29]  H. Gibson,et al.  Kinetics of doping and degradation of polyacetylene by oxygen , 1981 .

[30]  T. Tani,et al.  Phototransport effects in polyacetylene, (CH)x , 1980 .

[31]  J. Chien,et al.  Semiconducting poly(monocyanoacetylenes) , 1984 .

[32]  G. Del Re,et al.  Self-Consistent-Field Tight-Binding Treatment of Polymers. I. Infinite Three-Dimensional Case , 1967 .

[33]  B. Binggeli,et al.  Polypyrrole for use in information storage , 1985 .

[34]  K. Yoshino,et al.  Electrical and Optical Properties of Polythiophene Irradiated with Electron Beam in the Presence of SF6 and Their Application as Radiation Detector , 1984 .

[35]  K. Kanazawa,et al.  Electrochemical polymerization of pyrrole , 1979 .

[36]  P. Nigrey,et al.  Lightweight Rechargeable Storage Batteries Using Polyacetylene, ( CH ) x as the Cathode‐Active Material , 1981 .

[37]  K. Fukui,et al.  The electronic structures of fluorinated polyacetylenes. A design of new organic polymer alternatives to polyacetylene , 1980 .