Dynamical Behavior and Dipole–Dipole Interactions of Tetrafluoromethane–Water

Lone‐Pair⋅⋅⋅π Interaction: A Rotational Study of the Chlorotrifluoroethylene–Water Adduct

“…This is, to our knowledge, the first time that this interaction is observed and described through a rotational study in a molecular complex. Comparing our results to those obtained by rotational studies of ethylene-water, [13] benzene-water, [14] tetrafluoromethane-water, and chlorotrifluoromethanewater adducts, [12] we can state that this kind of interactionin competition with hydrogen bonds and halogen bondstakes place when water is interacting with perhalogenated alkenes.…”

“…[12] The geometries of the adducts of water with molecules containing a p-electron system, such as ethylene-water [13] and benzene-water [14] have been found to be stabilized by OH···p interactions, although with high dynamical effects.…”

Disorder of Hydrofluorocarbon Molecules Entrapped in the Water Cages of Structure I Clathrate Hydrate

“…Theoretical calculations suggest the occurrence of blueshifted hydrogen bonds between hydrogen of the HFCs and H 2 O, but other theoretical calculations and structural and energetic analyses suggest that the fluorine atoms in the HFCs may act as hydrogen-bond acceptors in ac omplex with water,a lthough neither of these theoretical modelsa re for guests in clathrate hydrate. [36][37][38][39][40] These two possibilities probably contribute to large guest molecules being too large to fit into the 5 12 cages. One other effect of increased host-guest interactions, which are likelyt o result from hydrogen bonding, is the greater mobility of water molecules, as demonstrated by decreased activation energies for water reorientation.…”

Internal Dynamics in Halogen‐Bonded Adducts: A Rotational Study of Chlorotrifluoromethane–Formaldehyde

“…[1] Details of the nature of the HaB in the gas phase, as obtained from rotational studies of molecular complexes of small inorganic molecules with water, have been reviewed by Legon. [2] The HaBs formed between water and perhalogenated freons are described in two studies on CF 4 ÀH 2 O [3] and CF 3 ClÀH 2 O. [4] More recently, we have shown, through the rotational spectrum of chlorotrifluoroethylenewater (C 2 ClF 3 ÀH 2 O), that water links to a fully halogenated alkene molecule by the contact of the oxygen lone pair (lp) of electrons with the alkene p system (i.e., the Bürgi-Dunitz n···p* interaction).…”