First-principles calculations of the three-dimensional structure and intrinsic defects in trans -polyacetylene

Journal Article · Fri Jun 15 04:00:00 EDT 1990 · Physical Review, B: Condensed Matter; (USA)

DOI:https://doi.org/10.1103/PhysRevB.41.12797· OSTI ID:6739367

Vogl, P; Campbell, D K ^[1]

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1. Center for Nonlinear Studies, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (USA)

We report a first-principles, local-density-functional (LDA) calculation of the electronic structure of crystalline, three-dimensional (3D) {ital trans}-(CH){sub {ital x}}. For the perfect crystal, we find a broken-symmetry ground state having {ital P}2{sub 1}/{ital a} space-group symmetry, corresponding to {ital in}-phase dimerization on neighboring chains within the unit cell. We show that in this structure the interchain couplings, although weak, lead to an asymmetry between the valence and conduction bands and, more importantly, give 3D character to the electronic band-edge states. We investigate several additional aspects of the electronic structure of the perfect crystal, including self-consistent optimization of the ions in the unit cell, spin polarization and electronic charge densities, interchain electron-phonon interactions, and the density of states. To study intrinsic defects in {ital trans}-(CH){sub {ital x}}, we map our LDA results onto a multi-orbital, tight-binding model; this mapping preserves very accurately all the electronic-structure properties of the full calculation. Using a Koster-Slater Green-function technique, we are able to examine both (shallow) polaronlike and (deep) bipolaronlike lattice distortions corresponding to localized defects. We find that the 3D character of the electronic band-edge states strongly suppresses the formation of the self-trapped, localized defects characteristic of the 1D models, destabilizing polarons and possibly bipolarons as well in perfectly ordered 3D {ital trans}-(CH){sub {ital x}}. To establish a connection with earlier work, we demonstrate that by artificially decreasing interchain effects and/or increasing the intrachain electron-phonon coupling we can cause polarons and bipolarons to form.

• OSTI ID: 6739367
• Journal Information: Physical Review, B: Condensed Matter; (USA), Journal Name: Physical Review, B: Condensed Matter; (USA) Vol. 41:18; ISSN 0163-1829; ISSN PRBMD
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360603* -- Materials-- Properties
CALCULATION METHODS
CRYSTAL DEFECTS
CRYSTAL STRUCTURE
CRYSTALS
ELECTRONIC STRUCTURE
HYDROCARBONS
MATERIALS
ORGANIC COMPOUNDS
ORGANIC SEMICONDUCTORS
POLYACETYLENES
POLYENES
SEMICONDUCTOR MATERIALS