Asymmetrically solvated anion with both kinetic and thermodynamic stabilities: Theoretical studies on the cluster anions (HF)n - (n=3-6).
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.
Hao
Xi-Yun
XY
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, Fujian, People's Republic of China.
Xu
Xin
X