Ling-Ling Lv

CH4 activation by W atom in the gas phase: a case of two-state reactivity process.

Gas-phase methane activation by tungsten (W) atoms was studied at the density functional level of theory using the hybrid exchange correlation functional B3LYP. Four reaction profiles corresponding to the septet, quintet, triplet, and singlet multiplicities were investigated in order to ascertain the presence of some spin inversion during the methane activation. Methane activation mediated by W atoms was found to be a spin-forbidden process resulting from the crossing among the multistate energetic profiles. On the basis of the Hammond postulate, this is a typical two-state reactivity (TSR) reaction. The minimum energy crossing points lead to decrease in the barrier heights of TS01, TS12, TS23, and TS24 that correspond to the first, second, and third hydrogen transfer and the reductive elimination step of H(2), respectively. The spin-orbit coupling is calculated between electronic states of different multiplicities at the crossing points (MECPs) to estimate the intersystem crossing probabilities, and the probability of hopping from one surface to the other in the vicinity of the crossing region is calculated by the Landau-Zener type model.

Designation and Exploration of Halide-Anion Recognition Based on Cooperative Noncovalent Interactions Including Hydrogen Bonds and Anion-π.

A novel urea-based anion receptor with an electron-deficient aromatic structural unit, N-p-nitrophenyl-N-(4-vinyl-2-five-fluoro-benzoic acid benzyl ester)-phenyl-urea (FUR), was designed to probe the potential for halide-anion recognition through the cooperation of two distinct noncovalent interactions including hydrogen bonds and anion-π in this work. The nature of the recognition interactions between halide-anion and the designed receptor was theoretically investigated at the molecular level. The geometric features of the hydrogen bond and anion-π of the FUR@X(-) (X = F, Cl, Br, and I) systems were thoroughly investigated. The binding energies and thermodynamic information on the halide-anion recognitions show that the presently designed FUR might selectively recognize anion F(-) based on the cooperation of the N-H···F(-) hydrogen bond and anion-π interactions both in vacuum and in solvents. IR and UV-visible spectra of free FUR and FUR@F(-) have been simulated and discussed qualitatively, which may be helpful for further experimental investigations in the future. Additionally, the electronic properties and behaviors of the FUR@X(-) systems were discussed according to the calculations on the natural bond orbital (NBO) data, molecular electrostatic potential (MEP), and weak interaction regions.