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Theoretical study of the H/D isotope effect on phase transition of hydrogen-bonded organic conductor κ-H3(Cat-EDT-TTF)2.
- Source :
- Physical Chemistry Chemical Physics (PCCP); 11/21/2016, Vol. 18 Issue 43, p29673-29680, 8p
- Publication Year :
- 2016
-
Abstract
- κ-H<subscript>3</subscript>(Cat-EDT-TTF)<subscript>2</subscript> (H-TTF) is a hydrogen-bonded π-electron system which was found to reveal C2/c symmetry at 50–293 K, while its isotopologue, κ-D<subscript>3</subscript>(Cat-EDT-TTF)<subscript>2</subscript> (D-TTF), showed the phase transition at 185 K from C2/c to P1̅. To elucidate the origin of such a difference, we calculated the potential energy curves (PECs) for the hydrogen transfer along the H-bonds in these conductors. We found that both the π-stacking and the hydrogen nuclear quantum effect drastically affected the hydrogen transfer energy. By taking account of both effects, we obtained a symmetric single-well effective PEC for H-TTF, which indicated that the hydrogen was always located at the center of the H-bond. By contrast, the effective PEC of D-TTF was a low-barrier double-well, indicating that the position of the H-bonded deuterium would change according to the temperature. We concluded that the π-stacking and the nuclear quantum effect were the key factors for the appearance of phase transition only in D-TTF. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14639076
- Volume :
- 18
- Issue :
- 43
- Database :
- Complementary Index
- Journal :
- Physical Chemistry Chemical Physics (PCCP)
- Publication Type :
- Academic Journal
- Accession number :
- 119218331
- Full Text :
- https://doi.org/10.1039/c6cp05414e