Electronic and optical properties of functionalized carbon chains with the localized Hartree-Fock and conventional Kohn-Sham methods
Weimer M, Hieringer W, Della Sala F, Görling A (2005)
Publication Type: Journal article, Original article
Publication year: 2005
Journal
Original Authors: Weimer M., Hieringer W., Sala F.D., Görling A.
Publisher: Elsevier
Book Volume: 309
Pages Range: 77-87
DOI: 10.1016/j.chemphys.2004.05.026
Abstract
The electronic and optical properties of extended functionalized carbyne chains, polyynes and cumulenes, are investigated with the localized Hartree-Fock method, with conventional Kohn-Sham methods, and with the Hartree-Fock method. It is found that even for very long polyynes the carbon-carbon bond lengths within a polyyne alternate while for long cumulenes no carbon-carbon bond length alternation occurs. Polyynes exhibit a finite HOMO-LUMO gap even if they become very long while cumulenes are found to become metallic in the limit of long chain lengths. The geometry and the electro-optical properties of polyynes cannot be influenced significantly by simple sp-σ-bonded end groups. The optically active Σ←X Σ electronic transition in polyynes is investigated by time-dependent density-functional theory (TDDFT). The known systematic underestimation of excitation energies in large chain-like systems by TDDFT methods is also found for the systems considered here. Deficiencies in the commonly used exchange-correlation kernels are identified as the main source of this shortcoming of TDDFT methods. Unphysical Coulomb self-interactions present in conventional Kohn-Sham potentials seem to not contribute significantly to the problem. © 2004 Elsevier B.V. All rights reserved.
Authors with CRIS profile
Wolfgang Hieringer
Lehrstuhl für Theoretische Chemie
Andreas Görling
Lehrstuhl für Theoretische Chemie
Involved external institutions
Italy (IT)How to cite
APA:
Weimer, M., Hieringer, W., Della Sala, F., & Görling, A. (2005). Electronic and optical properties of functionalized carbon chains with the localized Hartree-Fock and conventional Kohn-Sham methods. Chemical Physics, 309, 77-87. https://dx.doi.org/10.1016/j.chemphys.2004.05.026
MLA:
Weimer, Martin, et al. "Electronic and optical properties of functionalized carbon chains with the localized Hartree-Fock and conventional Kohn-Sham methods." Chemical Physics 309 (2005): 77-87.
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