A bridged tetrahedryl-tetrahedrane ("TT") was, theoretically, recognized as the holder of the chemical record for the shortest C-C single bond in a stable molecule. However, owing to its strained nature, this molecule is prone to rearrange to a carbene via ring contraction. Although TT was predicted to be stable to rearrangement at very low temperatures, our calculations find that, due to carbo...

Hydrocarbon cages are key reference materials for the validation and parameterization of computationally cost-effective procedures such as density functional theory (DFT), semiempirical molecular orbital theory, and molecular mechanics. We obtain accurate total atomization energies (TAEs) and heats of formation (Δf H°298) for platonic and prismatic hydrocarbon cages by means of the Wn-F12 expli...

The bond energy (BE) of CC in CH3-CH3 with respect to geometry frozen fragments follows a sigmoidal increase as function the θ = HCC pyramidalization angle. Using dynamic orbital forces BE index, same behaviour unique 〈θ〉 parameter, mean angle substituents, is found for 24 single bonds various hydrocarbons. Thus parameter appears straightforward and robust index geometrical constraints which ca...

In the present work, an amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) chiral stationary phase (CSP) was prepared by coating ADMPC on small-particle silica gel. This ADMPC-CSP was for the first time successfully applied to separate a series of novel chiral metal tetrahedrane-type clusters. Furthermore, the influence of a mobile-phase modifier (various alcohols added in the mobile phase), inc...

Recent work has resulted in the discovery of the fluorocarbyne complex (eta(5)-C(5)H(5))Mo(CO)(2)(CF), in which the CF ligand behaves as a formal three-electron donor like the isoelectronic well-known NO ligand. In this connection the related fluorocarbyne cobalt carbonyls Co(CF)(CO)(n) (n = 3, 2, 1) and Co(2)(CF)(2)(CO)(n) (n = 6, 5, 4, 3, 2) have been studied by density functional theory. The...

In the framework of density functional theory (DFT) simulations molecules and materials, anharmonic terms potential energy surface are commonly computed numerically, with an associated cost that rapidly increases size system. Recently, efficient approach to calculate cubic quartic interatomic force constants in basis normal modes [Theor. Chem. Acc., 120, 23 (2008)] was implemented Crystal progr...