PubMed Health⌕ Search

PubMed · 16740663

Multiple self-localized electronic states in trans-polyacetylene.

Abstract

Electronic structure calculations on a conjugated polymer chain by Hartree-Fock and density functional theory show a sequence of self-localized states, which stand in contrast to the single self-localized soliton state described by the Su-Schrieffer-Heeger model Hamiltonian. An extended Hubbard model, which treats electron-electron interactions up to second neighbors, is constructed to demonstrate that the additional states arise from a strong band-bending effect due to the presence of localized electric fields of charged solitons. We suggest the optical response of these electronic states may be associated with the near-edge oscillations observed in photo-induced absorption spectra. Our calculations indicate further that in the presence of counterions, the additional localized states continue to exist. Implications regarding soliton mobility and high-resolution ion sensing are briefly discussed.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Xi Lin, Ju Li, Clemens J Först, Sidney Yip. 2006-06-01. Multiple self-localized electronic states in trans-polyacetylene.. https://doi.org/10.1073/pnas.0601314103

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related citations

Highly selective Diels-Alder reactions of directly connected enyne dienophiles.

The paper describes the course of cycloadditions of Diels-Alder dienophiles containing linked enyne sites, each substituted with activating groups. Consistently, it was found that in the enyne cases the Diels-Alder reaction occurred specifically at the acetylenic center. Furthermore, it was found that the regiochemical sense of the cycloaddition was apparently determined by the remote activating group bound to the olefinic site. This remote acrylyl group totally dominated the course of the cycloaddition, relative to the activating group bound directly on the acetylene site. Explanations for these findings at the computational level are provided. The computations also rationalize the strong preference for cycloaddition to occur at the acetylene linkage and encompass the otherwise surprising regiochemical dominance by the remote ester on the olefinic site. The high selectivities available through such reactions provide important new opportunities in the synthesis of orsenillate type substructures that are found in a variety of natural products of contemporary interest.

Acetylene↗

Enantioselective phenylacetylene addition to aldehydes and ketones catalyzed by recyclable polymeric Zn(salen) complex.

New polymeric Zn(salen) complex was employed in the enantioselective phenylacetylene addition to aldehydes and ketones to produce corresponding chiral secondary propargylic alcohols with yields (up to 96%) and enantioselectivity (up to 72%) and tertiary propargylic alcohols with yields (up to 79%) and enantioselectivity (up to 68%) at room temperature, with added advantage of four times reuse with retention of enantioselectivity.

Acetylene↗

Using triethynylphosphine ligands bearing bulky end caps to create a holey catalytic environment: application to gold(I)-catalyzed alkyne cyclizations.

The synthesis, properties and catalytic uses of phosphinoalkynes bearing bulky end caps at the alkyne termini, that is, tris[(triarylsilyl)ethynyl]phosphines are reported. The most salient feature of the new phosphines is the holey molecular shape possessing a deep and large-scale metal-binding cavity. The holey phosphines displayed remarkable rate enhancement in the gold(I)-catalyzed six- and seven-membered ring forming cyclizations of acetylenic keto esters and 1,7-enynes. It is proposed that the cavity in the ligand forces a nucleophilic center (enol or alkene) of the acetylenic compounds close to the gold-bound alkyne, making ring-closing anti attack feasible.

Acetylene↗