Ground state of<i>trans</i>-polyacetylene and the Peierls mechanism

Ashkenazi, J.; Pickett, W. E.; Krakauer, Henry; Wang, C. S.; Klein, Bern; Chubb, S. R.

doi:10.1103/physrevlett.62.2016

Cited by 82 publications

(32 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The exceptional character of PA and PDA with respect to both the large differences in relaxation energy for the B u and A g excitons and the role of four-particle excitations seems to be in line with the fact that the description of their ground state geometries is also extremely complicated, 17,18 which is also an exception, as discussed earlier in Sec. II A.…”

Section: The a G -B U Exciton Order In Pa And Pdasupporting

confidence: 69%

“…DFT calculations ͑in this case within the local density approximation, referred to as DFT-LDA͒ generally yield reliable results for covalent bonds ͑errors in length and angle Ͻ1%͒. Such calculations have been shown to fail for PA, 17 yielding a too small dimerization of the sp 2 carbon-carbon bonds in the backbone. While inclusion of many-body correlations in the calculation of the geometry can resolve this error, 18 we take the geometry of PA and PDA ͑for which we found the same problem to occur͒ from experiment.…”

Section: A Geometrymentioning

confidence: 99%

See 1 more Smart Citation

Calculation of excitonic properties of conjugated polymers using the Bethe–Salpeter equation

Horst

Bobbert

Michels

et al. 2001

The Journal of Chemical Physics

119

View full text Add to dashboard Cite

DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User Agreement:

show abstract

Section: The a G -B U Exciton Order In Pa And Pdasupporting

confidence: 69%

Section: A Geometrymentioning

confidence: 99%

Calculation of excitonic properties of conjugated polymers using the Bethe–Salpeter equation

Horst

Bobbert

Michels

et al. 2001

The Journal of Chemical Physics

119

View full text Add to dashboard Cite

show abstract

“…polymer with two half-filled p bands. The symmetry breaking enables the formation of a gap, in analogy to the elusive case of trans-polyacetylene [10].…”

mentioning

confidence: 99%

Electron Correlation inC4N+2Carbon Rings: Aromatic versus Dimerized Structures

2000

View full text Add to dashboard Cite

The electronic structure of C(4N+2) carbon rings exhibits competing many-body effects of Huckel aromaticity, second-order Jahn-Teller (SOJT), and Peierls instability at large sizes. This leads to possible ground state structures with aromatic, bond angle, or bond length alternated geometry. Highly accurate quantum Monte Carlo results indicate the existence of a crossover between C10 and C14 from bond angle to bond length alternation. The aromatic isomer is always a transition state. The gap opening mechanism is the SOJT effect, which coalesces with the Peierls regime as N-->infinity.

show abstract

“…As far as we are aware, all current-density functionals predict that polyacetylene has no bond-length alternation (see, e.g., Refs. [23][24][25][26][27], and hence has no band gap and is metallic in nature. Extended systems such as porphyrins are depicted as having unphysically large numbers of low-energy valence excited states, and calculations of donor-bridge-acceptor coupling through π bridges using sophisticated density functionals such as B3LYP to asymptotically predict 27 metallic-like behavior for large bridging molecules.…”

Section: Implications For Density Functional Calculations Of Through-mentioning

confidence: 99%

“…This leads to overestimation of the metallic nature of molecular wires, with, for example, polyacetylene being depicted as metallic. [23][24][25][26] We have observed profound consequences of this in intramolecular electron transport through molecular wires, 27 and it is quite possible that electrode-molecule-electrode conduction will be found to be one of the few areas in which use of DFT is not particularly apt.…”

Section: Introductionmentioning

confidence: 99%

An Atomistic Approach to Conduction Between Nanoelectrodes Through a Single Molecule

Reimers

Shapley

Lambropoulos

et al. 2002

Annals of the New York Academy of Sciences

View full text Add to dashboard Cite

Capacitance and other properties of nanoelectrodes, finite-size metal clusters envisaged for use in complex molecular-electronic devices, are discussed. The applicability of classical electrostatics (Coulomb's and Gauss' law, Poisson's equation, etc.) to atomistic systems is investigated and the self-energy necessary to store a finite charge on an atom is found to be of central importance. In particular, the neglect of electron exchange is found to introduce severe limitations, with quantum calculations predicting fundamentally different electronic structures. Also, the well-known poor representation of the atomic self-energy inherent to modern DFT is discussed, along with its implications for molecular electronics calculations. An INDO/S method is introduced with new parameters for gold. This is the simplest approximate computational scheme that correctly includes quantum electrostatic, resonance, and spin effects, and is capable of describing arbitrary excited electronic states. Encouraging results are obtained for some trial problems. In particular, voltage differential between the electrodes in electrode-molecule-electrode conduction is obtained, not through an a priori prescription but rather by moving whole electrons between the electrodes and analyzing the response. The voltage drops across the molecule-electrode junctions and the central molecular region are then deduced. This alternative to the current Landauer-based 1-particle transmission equations for electrode-molecule-electrode conduction is discussed in terms of the use of the electronic states of the system. It provides a proper description not only of conduction via electrode-to-molecule charge or hole transfer but also of conduction via simultaneous charge and hole transfer via low-lying excited molecular electronic states, including the ability to account for electroluminescence and other chemical effects. In addition, various aspects of our research on the quantitative prediction of the I(V) curves for electrodemolecule-electrode conduction are reviewed, including demonstration of the equivalence of the formalisms generated by the Datta and the Mujica-Ratner groups, and the development of analytically solvable paradigms, including the conduction through a linear-chain Hückel wire.

show abstract

Ground state oftrans-polyacetylene and the Peierls mechanism

Cited by 82 publications

References 31 publications

Calculation of excitonic properties of conjugated polymers using the Bethe–Salpeter equation

Calculation of excitonic properties of conjugated polymers using the Bethe–Salpeter equation

Electron Correlation inC4N+2Carbon Rings: Aromatic versus Dimerized Structures

An Atomistic Approach to Conduction Between Nanoelectrodes Through a Single Molecule

Contact Info

Product

Resources

About