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Toward the parametrization of the Hubbard model for salts of bis(ethylenedithio)tetrathiafulvalene: A density functional study of isolated molecules

J. Chem. Phys. 130, 104508 (2009); doi:10.1063/1.3080543

Published 13 March 2009

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Edan Scriven and B. J. Powell
Centre for Organic and Photonic Electronics, School of Physical Sciences, University of Queensland, Queensland 4072, Australia
We calculate the effective Coulomb repulsion between electrons/holes U<sub>m</sub><sup>(v)</sup> and site energy for an isolated bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) molecule in vacuo. U<sub>m</sub><sup>(v)</sup>=4.2±0.1  eV for 44 experimental geometries taken from a broad range of conformations, polymorphs, anions, temperatures, and pressures (the quoted “error” is one standard deviation). Hence we conclude that U<sub>m</sub><sup>(v)</sup> is essentially the same for all of the compounds studied. This shows that the strong (hydrostatic and chemical) pressure dependence observed in the phase diagrams of the BEDT-TTF salts is not due to U<sub>m</sub><sup>(v)</sup>. Therefore, if the Hubbard model is sufficient to describe the phase diagram of the BEDT-TTF salts, there must be significant pressure dependence on the intramolecular terms in the Hamiltonian and/or the reduction in the Hubbard U due to the interaction of the molecule with the polarizable crystal environment. The renormalized value of U<sub>m</sub><sup>(v)</sup> is significantly smaller than the bare value of the Coulomb integral, F0=5.2±0.1  eV, across the same set of geometries, emphasizing the importance of using the renormalized value of U<sub>m</sub><sup>(v)</sup>. The site energy (for holes), xim=5.0±0.2  eV, varies only a little more than U<sub>m</sub><sup>(v)</sup> across the same set of geometries. However, we argue that this variation in the site energy plays a key role in understanding the role of disorder in bis(ethylenedithio)tetrathiafulvalene salts. We explain the differences between the betaL and betaH phases of (BEDT-TTF)2I3 on the basis of calculations of the effects of disorder. ©2009 American Institute of Physics
History: Received 31 October 2008; accepted 21 January 2009; published 13 March 2009
Permalink: http://link.aip.org/link/?JCPSA6/130/104508/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.E-
    Density-functional theory (atoms and molecules)
  • 33.15.Bh
    General molecular conformation and symmetry; stereochemistry
  • 33.15.Hp
    Molecular barrier heights (internal rotation, inversion, rotational isomerism, conformational dynamics)
  • YEAR: 2009

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0021-9606 (print)   1089-7690 (online)
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