Asymmetrically solvated anion with both kinetic and thermodynamic stabilities: Theoretical studies on the cluster anions (HF)(n)(-) (n=3-6)

摘要

At the level of MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets supplemented with diffuse bond functions, the authors searched the potential energy surfaces of (HF)(n)(-) (n=3-6). In accordance with the literature, they found that the symmetrically solvated-electron anion (3(FH){e}) possesses the largest vertical detachment energy (VDE), while the dipole-bound anion ((FH)(3){e}) is the lowest isomer in energy for (HF)(3)(-). Their calculations demonstrated that, with the increase of the cluster size, the asymmetric (FH)(a){e}(HF)(b) cluster is stabilized with a simultaneously increased VDE. Thus they predicted that, for (HF)(6)(-), the (FH)(4){e}(HF)(2) cluster is both kinetically and thermodynamically most stable, possessing the largest VDE and being the global minimum at the same time. (c) 2007 American Institute of Physics.