Thioamides and selenoamides are better hydrogen-bond donors than carboxamides because their amino groups more positively charged. Quantum chemical analyses reveal that this counterintuitive phenomenon, which cannot be explained by the electronegativity, originates from larger electronic density flow nitrogen lone pair of NH2 group towards lower-lying π* orbital on C=S or C=Se bond. This differe...

The Cover Feature shows how understanding the growth of linear molecular chains is key for rational design and synthesis novel supramolecular materials. Using state-of-the-art quantum chemical computations, this work demonstrates that cooperative properties halogen bonds in can be rationalized by increased charge separation within σ-electronic system, resulting from a stronger transfer lone-pai...

We report the geometric and electronic effects of amine (with one lone pair electron) and thiol (with two lone pair electrons) ligands on the structural transformation of Pt(55) nanoparticles (NPs) by first-principles calculation. Although a cuboctahedral (COh) structure is less stable than an icosahedral (Ih) structure by 1.36 eV for a bare Pt(55) NP, the activation barrier from the COh to the...

A number of novel hydrocarbon cage systems have been designed and characterized using ab initio molecular orbital calculations at the MP2 and B3-LYP levels. In particular, equilibrium structures for five families of molecules, hemialkaplanes, hemispiroalkaplanes, alkaplanes, spiroalkaplanes and dimethanospiroalkaplanes, have been examined in detail with the aim of designing a saturated hydrocar...

Bond dissociation energies (BDEs) of neutral HgX and cationic HgX(+) molecules range from less than a kcal mol(-1) to as much as 60 kcal mol(-1). Using NESC/CCSD(T) [normalized elimination of the small component and coupled-cluster theory with all single and double excitations and a perturbative treatment of the triple excitations] in combination with triple-zeta basis sets, bonding in 28 mercu...