First-principles study of spontaneous polarization in tetrathiafulvalene-p-chloranil (TTF-CA)

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Abstract We have performed first-principles calculations on the organic compound tetrathiafulvalene-p-chloranil (TTF-CA: TTF = C 6 H 4 S 4 , CA = C 6 Cl 4 O 2 ) in order to evaluate its spontaneous polarization. The obtained value on the experimental structure is 0.10 C / m 2 while it is 0.12 C / m 2 on the structure with the computationally optimized atomic positions. These values are significantly larger than the existing experimental value of 0.4 × 10 ‐ 2 C / m 2 [E. Collet, Ph.D. Thesis, University of Rennes 1, 1999]. The origin of the calculated large spontaneous polarization is discussed.

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