Theoretical study of the H/D isotope effect on phase transition of hydrogen-bonded organic conductor κ-H3(Cat-EDT-TTF)2

Literature Information

Publication Date 2016-10-06
DOI 10.1039/C6CP05414E
Impact Factor 3.676
Authors

Kaichi Yamamoto, Yusuke Kanematsu, Umpei Nagashima, Akira Ueda, Hatsumi Mori, Masanori Tachikawa


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Abstract

κ-H3(Cat-EDT-TTF)2 (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-D3(Cat-EDT-TTF)2 (D-TTF), showed the phase transition at 185 K from C2/c to P. 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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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