Chirality and Relativistic Effects in Os3(CO)12

被引:1
作者
Ryzhikov, Maxim R. [1 ]
Mirzaeva, Irina V. [1 ]
Kozlova, Svetlana G. [1 ]
Mironov, Yuri V. [1 ]
机构
[1] RAS, SB, Nikolaev Inst Inorgan Chem, 3 Acad Lavrentiev Ave, Novosibirsk 630090, Russia
关键词
structure of the Os-3(CO)(12) clusters; chirality; relativistic effects; parity violating energy difference; quantum chemistry; ORDER REGULAR APPROXIMATION; ELECTRON LOCALIZATION; TOPOLOGICAL ANALYSIS; PARITY VIOLATION; AB-INITIO; DENSITY; PHOTOCHEMISTRY; OS3(CO)12; CLUSTER; STATE;
D O I
10.3390/molecules26113333
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The energy and structural parameters were obtained for all forms of the carbonyl complex of osmium Os-3(CO)(12) with D-3h and D-3 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 Os-3(CO)(12) corresponds to the D-3 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 similar to 10(-14) kJ/mol. Parity violation energy difference (PVED) between D-3(S) and D-3R states equals to similar to 5 x 10(-10) kJ/mol. An unusual three-center exchange interaction was found inside the {Os-3} 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.
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页数:10
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