Abstract

The energy and structural parameters were obtained for all forms of the carbonyl complex of osmium Os3(CO)12 with D3h 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 (D3S) or right-twisted (D3R). The D3S↔D3R transitions occur through the D3h transition state with an activation barrier of ~10–14 kJ/mol. Parity violation energy difference (PVED) between D3S and D3R 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.

Highlights

  • It is well known that enantiomerism is directly related to the origin of life on Earth.Many essential biological and chemical processes are stereoselective, involving only one enantiomer, which exists independently from its chiral counterpart

  • There were expectations that Metal-organic Frameworks (MOFs) with a DABCO linker may undergo a number of phase transitions related to enantiomers ordering [2,10], and that cooperative effects in such systems may help the experimental search of molecular parity violation effects [7,9,11]

  • We investigated what exactly is responsible for the stabilization of the twisted D3 structure compared to the untwisted D3h one

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Summary

Introduction

It is well known that enantiomerism is directly related to the origin of life on Earth. Especially interesting is how the parity violating weak nuclear forces may manifest in chiral molecules and may be somehow responsible for the choice of which enantiomer would prevail in living organisms [4,5,6,7]. There were expectations that MOFs with a DABCO linker may undergo a number of phase transitions related to enantiomers ordering [2,10], and that cooperative effects in such systems may help the experimental search of molecular parity violation effects [7,9,11]. To the DABCO molecule, trinuclear transition metal cluster complexes may have D3 symmetry. We expected that due to the cooperative effects, such trinuclear transition metal clusters may become a good family of systems for the experimental molecular parity violation search

Results and Discussion
The for the
D Dstructures characterizes the barrier between
Chirality
Geometry
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