查看更多>>摘要：The unlikely role of nitrogen in NH3 as an electron accepting pnicogen has been observed experimentally using matrix isolation infrared spectroscopy and computationally. Nitrogen hosts twin H-N...Cl pnicogen bonds, which enhance the stabilization of a dominantly Cl-P...N phosphorus bonded PCl3-NH3 heterodimer. The Cl-P...N phosphorus bond is proven to operate via the prominent sigma-holes of phosphorus whilst the H-N...Cl pnicogen bonds appear to be driven by dispersion. The possibility of nitrogen in NH3, a popular Lewis base, acting as an electron acceptor, reveals a thus far unexpected scenario: pnicogen bonds operating even in the absence of sigma/pi-holes.
查看更多>>摘要：The title reaction was investigated by DFT calculations. This process realizes in two steps. In the first step, singlet and triplet potential energy surfaces cross each other. We found that two-state reaction (TSR) mechanism is involved, enabling singlet product to be favored energetically. Then, ThO continues to react with H2O to form ThO2. Only the activation energy of singlet addition-elimination channel matches well with experimental reports. This work illustrates the occurrence of TSR mechanism in the corrosion of actinide nuclear fuel and further suggests a potential yet crucial impact on related fields. It deserves particular attention.
NSTL
Elsevier