1."Conformational lock" via unusual intramolecular C-FO[double bond, length as m-dash]C and C-HCl-C parallel dipoles observed in in situ cryocrystallized liquids.
Dey D1, Bhandary S1, Sirohiwal A1, Hathwar VR2, Chopra D1. Chem Commun (Camb). 2016 May 5. [Epub ahead of print]
We report an unusual intramolecular C-FO[double bond, length as m-dash]C and C-HCl-C parallel dipole-dipole alignment which "locks" the molecular conformation of cryocrystallized liquids towards planarity where the diatropic ring current establishes the existence of aromaticity in the five-membered ring associated with FO contact. Topological analysis establishes the bonding interaction between [F, O] and [H, Cl].
2.Rate Coefficients of the HCl + OH → Cl + H2O Reaction From Ring Polymer Molecular Dynamics.
Zuo J, Li Y, Guo H, Xie D. J Phys Chem A. 2016 May 5. [Epub ahead of print]
Thermal rate coefficients at temperatures between 200 and 1000 K are calculated for the HCl + OH → Cl + H2O reaction on a recently developed permutation invariant potential energy surface, using ring polymer molecular dynamics (RPMD). Large deviations from the Arrhenius limit are found at low temperatures, suggesting significant quantum tunneling. Agreement with available experimental rate coefficients is generally satisfactory, although the deviation becomes larger at lower temperatures. The theory-experiment discrepancy is attributed to the remaining errors in the potential energy surface, which is known to slightly overestimate the barrier. In the deep tunneling region, RPMD performs better than traditional transition-state theory with semi-classical tunneling corrections.
