A nonempirical effective Hamiltonian technique for polymers: Application to polyacetylene and polydiacetylene

The recently proposed ab initio effective Hamiltonian technique is extended to polymer calculations and applied to various conformations of polyacetylene (all‐trans, cis‐transoid, and trans‐cisoid) and polydiacetylene (acetylenic and butatrienic backbones). Band structures, density of states (DOS), and XPS theoretical spectra are presented. Comparison of the band structures and DOS with those obtained by ab initio SCF (self‐consistent‐field) Hartree–Fock calculations of double zeta quality is excellent. The XPS theoretical spectrum for all‐trans polyacetylene is in good agreement with experiment. In polyacetylene, it is found that the π bands are quite similar for all three backbone conformations, though the σ bands differ significantly. For polydiacetylene, low ionization potentials are predicted—a few tenths of an eV larger than polyacetylene for the acetylenic backbone and a few tenths of an eV smaller than polyacetylene for the butatrienic backbone.

[1]  L. Piela,et al.  Multipole expansion in tight-binding Hartree-Fock calculations for infinite model polymers , 1980 .

[2]  A. Karpfen.  Ab initio studies on polymers. IV. Polydiacetylenes , 1980 .

[3]  M. L. Shand,et al.  Three-wave mixing in conjugated polymer solutions: Two-photon absorption in polydiacetylenes , 1980 .

[4]  S. Suhai.  A priori electronic structure calculations on highly conducting polymers. I. Hartree–Fock studies on cis‐ and trans‐polyacetylenes (polyenes) , 1980 .

[5]  R. Chance.  Chromism in Polydiacetylene Solutions and Crystals , 1980 .

[6]  J. Delhalle,et al.  Conformational origin of peak structure arising in the XPS Spectrum of an isotactic polypropylene , 1979 .

[7]  W. R. Salaneck,et al.  Photoelectron spectra of AsF5‐doped polyacetylenes , 1979 .

[8]  G. G. Miller,et al.  Highly conducting charge‐transfer complexes of poly(p‐phenylene) , 1979 .

[9]  A. Karpfen,et al.  Ab initio Studies on polymers , 1979 .

[10]  P. Durand,et al.  A new general methodology for deriving transferable atomic potentials in molecules , 1979 .

[11]  R. Baughman,et al.  The structures of cis‐polyacetylene and highly conducting derivatives , 1978 .

[12]  R. Baughman,et al.  Thermochromism in a polydiacetylene crystal , 1977 .

[13]  R. Chance,et al.  Electronic structure of the polydiacetylenes: effect of bond length variations in a model system , 1977 .

[14]  D. Peeters,et al.  The linear combination of localized orbitals methods (LCLO) for polymers , 1977 .

[15]  M. Kertész,et al.  Ab initio Hartree–Fock crystal orbital studies. Energy bands in polyene reconsidered , 1977 .

[16]  J. Knecht.  XPS-valence band study of polydiacetylene-bis(toluenesulfonate) , 1977 .

[17]  J. Delhalle,et al.  Computation of the electronic density of states distributions of stereoregular polymers , 1977 .

[18]  H. Shirakawa,et al.  Thermal cis–trans isomerization and decomposition of polyacetylene , 1975 .

[19]  P. Durand,et al.  New atomic pseudopotentials for electronic structure calculations of molecules and solids , 1974 .

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

[21]  J. André,et al.  All‐electrons band structure of Polyene , 1971 .

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

[23]  R. Pitzer.  Optimized Molecular Orbital Wavefunctions for Methane Constructed from a Minimum Basis Set , 1967 .

[24]  J. Brédas,et al.  An FSGO-CO study of the long-range effects on calculated conformational stability and on one-electron levels of polyethylene , 1980 .

[25]  J. André.  Quantum Mechanical Methods for Regular Polymers , 1980 .

[26]  Jean-Marie André,et al.  Recent advances in the quantum theory of polymers : proceedings of the workshop held in Namur (Belgium), February 11-14, 1979 , 1980 .

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

[28]  A. Karpfen,et al.  Ab initio studies on all-trans-polyene☆ , 1979 .

[29]  Jean-Marie André,et al.  B.I.P. an interactive graphic system for indexing energy bands of model polymers , 1979, Comput. Chem..

[30]  Jean-Jacques Pireaux,et al.  Electronic structure of linear fluoropolymers: Theory and ESCA measurements revisited , 1977 .

[31]  B. O'Leary,et al.  Utilization of Transferability in Molecular Orbital Theory , 1975 .