First-principles studies of the structural and optical properties of crystalline poly(para-phenylene).

We present first-principles local-density band structure calculations for one-dimensional and three-dimensional crystalline poly (para-phenylene) (PPP) using the full-potential linearized augmented-plane-wave and the pseudopotential methods. Optimized structural parameters for PPP chains and for orthorhombic crystalline phases with space groups Pbam and Pnnm are determined. A torsion angle of 27\ifmmode^\circ\else\textdegree\fi{} is predicted in PPP chains and 17\ifmmode^\circ\else\textdegree\fi{} in the crystals. The dielectric tensor and the absorption coefficient are calculated. We find very good agreement with experimental data, indicating that the excitations are extended band states. The interchain coupling leads to energy band splittings of the order of 0.5 eV. It is shown that the energy gap can be varied over a wide energy range by relatively small structural modifications.

[1]  R. N. Marks,et al.  Light-emitting diodes based on conjugated polymers , 1990, Nature.

[2]  R. Grubbs,et al.  Transition-metal-catalyzed polymerization of heteroatom-functionalized cyclohexadienes: stereoregular precursors to poly(p-phenylene) , 1992 .

[3]  Takakazu Yamamoto,et al.  Crystal structure of poly(p-phenylene) prepared by organometallic technique , 1992 .

[4]  J. G. Fripiat,et al.  Highly conducting polyparaphenylene, polypyrrole, and polythiophene chains: Anab initiostudy of the geometry and electronic-structure modifications upon doping , 1984 .

[5]  J. Brédas,et al.  Relationship between band gap and bond length alternation in organic conjugated polymers , 1985 .

[6]  A. Heeger,et al.  Nature of the primary photoexcitations in poly(arylene-vinylenes) , 1994 .

[7]  P. Kovacic,et al.  Polymerization of aromatic nuclei. XIII. X-ray analysis and properties of poly(p-phenylene) pellets , 1968 .

[8]  Wang,et al.  Ground state of trans-polyacetylene and the Peierls mechanism. , 1989, Physical review letters.

[9]  L. Kleinman,et al.  Self-consistent calculations of the energy bands and bonding properties of B sub 12 C sub 3 , 1990 .

[10]  J. Baudour.  Structural phase transition in polyphenyls. X : Potential barrier heights in crystalline polyphenyls and in gaseous biphenyl determined uniquely from diffraction data , 1991 .

[11]  A. Zunger,et al.  Self-interaction correction to density-functional approximations for many-electron systems , 1981 .

[12]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[13]  J. Fink.  Electronic structure of conducting polymers: investigations of oriented samples by electron energy-loss spectroscopy , 1987 .

[14]  W. Yelon,et al.  Structural phase transition in polyphenyls. IV. Double‐well potential in the disordered phase of p‐terphenyl from neutron (200 K) and X‐ray (room‐temperature) diffraction data , 1977 .

[15]  Martins,et al.  Structural and electronic properties of C60. , 1992, Physical review. B, Condensed matter.

[16]  P. Vogl,et al.  Optical properties and pressure studies of crystalline transpolyacetylene , 1991 .

[17]  R. Girlanda,et al.  Optical properties of semiconductors within the independent-quasiparticle approximation. , 1993, Physical review. B, Condensed matter.

[18]  J. Fink.  Recent Developments in Energy-Loss Spectroscopy , 1989 .

[19]  Ullrich Scherf,et al.  Polyarylenes and poly(arylenevinylenes), 7. A soluble ladder polymer via bridging of functionalized poly(p‐phenylene)‐precursors , 1991 .

[20]  Leonard Kleinman,et al.  Efficacious Form for Model Pseudopotentials , 1982 .

[21]  von Boehm J,et al.  Density-functional study of undoped and doped trans-polyacetylene. , 1993, Physical Review B (Condensed Matter).

[22]  M. Stamm,et al.  Crystal Structure of Undoped and Lithium-Doped Polyparaphenylene , 1985 .

[23]  M. Stamm,et al.  STRUCTURAL CHANGES IN POLYPARAPHENYLENE BY THE DOPING WITH AsF5 AND ALKALI METALS , 1983 .

[24]  J. Baudour,et al.  Structural transition in polyphenyls. II. The crystal structure of the high-temperature phase of quaterphenyl , 1976 .

[25]  G. Leising,et al.  Electroluminescence of “wide-bandgap” chemically tunable cyclic conjugated polymers , 1993 .

[26]  Campbell,et al.  First-principles calculations of the three-dimensional structure and intrinsic defects in trans-polyacetylene. , 1990, Physical review. B, Condensed matter.

[27]  J. Baudour,et al.  Structural phase transition in polyphenyls. VI. Crystal structure of the low-temperature ordered phase of p-quaterphenyl at 110 K , 1978 .

[28]  Louie,et al.  High-pressure structural and electronic properties of carbon. , 1987, Physical review. B, Condensed matter.

[29]  J. Mintmire,et al.  Local-density-functional approach to all-trans-polyacetylene , 1983 .

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

[31]  Warren E. Pickett,et al.  Pseudopotential methods in condensed matter applications , 1989 .

[32]  Zhu,et al.  Quasiparticle band structure of thirteen semiconductors and insulators. , 1991, Physical review. B, Condensed matter.

[33]  Martins,et al.  Efficient pseudopotentials for plane-wave calculations. , 1991, Physical review. B, Condensed matter.

[34]  C. Clews,et al.  An X‐ray and neutron diffraction refinement of the structure of p‐terphenyl , 1970 .

[35]  R. Car,et al.  Structure and properties of polymers calculated by Ab initio molecular dynamics , 1993 .

[36]  Chang,et al.  Pressure coefficients of band gaps of diamond. , 1987, Physical review. B, Condensed matter.

[37]  Conwell,et al.  Excitons and the band gap in poly(phenylene vinylene). , 1993, Physical review. B, Condensed matter.

[38]  Conwell,et al.  First-principles calculation of the three-dimensional band structure of poly(phenylene vinylene). , 1993, Physical review. B, Condensed matter.

[39]  J. Petermann,et al.  Paracrystalline Nature of Poly (p-Phenylene) , 1986 .

[40]  G. Wegner,et al.  Soluble poly(para‐phenylene)s, 3. Variation of the length and the density of the solubilizing side chains , 1990 .

[41]  Peter Blaha,et al.  Full-potential, linearized augmented plane wave programs for crystalline systems , 1990 .

[42]  R. O. Jones,et al.  The density functional formalism, its applications and prospects , 1989 .

[43]  B. Farmer,et al.  Crystal Structures, Phase Transitions and Energy Calculations of Poly(p-phenylene) Oligomers , 1993 .

[44]  I. Shirley,et al.  Synthesis of polyphenylene from a cis-dihydrocatechol biologically produced monomer , 1988 .

[45]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[46]  Fukumoto.  First-principles pseudopotential calculations of the elastic properties of diamond, Si, and Ge. , 1990, Physical review. B, Condensed matter.

[47]  Kurz,et al.  Ultrafast field-induced dissociation of excitons in conjugated polymers. , 1994, Physical review letters.

[48]  G. Lieser,et al.  Redox reactions of poly(1,4‐phenylene). A spectroscopic study of thin transparent films , 1982 .

[49]  Bruno Ullrich,et al.  Realization of a blue-light-emitting device using poly(p-phenylene)†‡ , 1992 .