TY - JOUR
T1 - Off-Planar Geometry and Structural Instability of EDO-TTF Explained by Using the Extended Debye Polarizability Model for Bond Angles
AU - Linker, Gerrit-Jan
AU - van Duijnen, Piet Th.
AU - van Loosdrecht, Paul H. M.
AU - Broer-Braam, Henderika
PY - 2012/7/5
Y1 - 2012/7/5
N2 - 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.
AB - 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.
KW - ELECTRON-DIFFRACTION
KW - PHASE-TRANSITION
KW - (EDO-TTF)(2)PF6
KW - FIELD
KW - TETRATHIAFULVALENE
KW - DIHALIDES
KW - GROUP-12
U2 - 10.1021/jp303967s
DO - 10.1021/jp303967s
M3 - Article
VL - 116
SP - 7219
EP - 7227
JO - The Journal of Physical Chemistry. A: Molecules, Spectroscopy, Kinetics, Environment, & General Theory
JF - The Journal of Physical Chemistry. A: Molecules, Spectroscopy, Kinetics, Environment, & General Theory
SN - 1089-5639
IS - 26
ER -