Off-Planar Geometry and Structural Instability of EDO-TTF Explained by Using the Extended Debye Polarizability Model for Bond Angles

Gerrit-Jan Linker*, Piet Th. van Duijnen, Paul H. M. van Loosdrecht, Henderika Broer-Braam

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

5 Citations (Scopus)
34 Downloads (Pure)

Abstract

The geometry of ethylenedioxy-tetrathiafulvalene, EDO-TTF, plays an important role in the metal-insulator transition in the charge transfer salt (EDO-TTF)(2)PF6. The planar and off-planar geometrical conformations of the EDO-TTF molecules are explained using an extended Debye polarizability model for the bond angle. The geometrical structure of EDO-TTF is dictated by its four sulfur bond angles and these are, in turn, determined by the polarizability of the sulfur atoms. With Hartree-Fock and second-order Moller-Plesset perturbation theory calculations on EDO-TTF, TTF, H2S, and their oxygen and selenium substituted counterparts we confirm this hypothesis. The Debye polarizability model for bond angles relates directly the optimum bond angle with the polarizability of the center atom. Considering the (EDO-TTF)(2)PF6 material in this light proves to be very fruitful.

Original languageEnglish
Pages (from-to)7219-7227
Number of pages9
JournalThe Journal of Physical Chemistry A
Volume116
Issue number26
DOIs
Publication statusPublished - 5-Jul-2012

Keywords

  • ELECTRON-DIFFRACTION
  • PHASE-TRANSITION
  • (EDO-TTF)(2)PF6
  • FIELD
  • TETRATHIAFULVALENE
  • DIHALIDES
  • GROUP-12

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