Chirality and Relativistic Effects in Os3(CO)12

Molecules

Maxim R. Ryzhikov¹  Yuri V. Mironov¹  Irina V. Mirzaeva¹  Svetlana G. Kozlova¹ 

[1] Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Acad. Lavrentiev Ave., 630090 Novosibirsk, Russia;

关键词: structure of the Os₃(CO)₁₂ clusters;    chirality;    relativistic effects;    parity violating energy difference;    quantum chemistry;   

DOI  :  10.3390/molecules26113333

来源: DOAJ

【 摘 要 】

The energy and structural parameters were obtained for all forms of the carbonyl complex of osmium Os₃(CO)₁₂ with D_3h and D₃ symmetries using density functional theory (DFT) methods. The calculations took into account various levels of relativistic effects, including those associated with nonconservation of spatial parity. It was shown that the ground state of Os₃(CO)₁₂ corresponds to the D₃ symmetry and thus may be characterized either as left-twisted (D_3S) or right-twisted (D_3R). The D_3S↔D_3R transitions occur through the D_3h transition state with an activation barrier of ~10^–14 kJ/mol. Parity violation energy difference (PVED) between D_3S and D_3R states equals to ~5 × 10⁻¹⁰ kJ/mol. An unusual three-center exchange interaction was found inside the {Os₃} fragment. It was found that the cooperative effects of the mutual influence of osmium atoms suppress the chirality of the electron system in the cluster.

【 授权许可】

Unknown