Nonempirical Description of the Atmospherically Important Anionic Species. I. Water Cluster Anions

Abstract

Water cluster anions, comprising up to 20 molecules, are simulated at the second-order unrestricted Moller–Plesset perturbation theory level with 6-31++G** basis set augmented with a floating center of 8 s diffuse functions. Interface structures composed of two to four chainlike or cyclic subclusters found to be most stable among anions of the same molecular size are shown to serve as a reliable restricted model of the hydrated electron. The calculated values of the adiabatic electron affinity of neutral clusters and the vertical energies of electron detachment from anions fit in with n−1/3 dependences that provide the corresponding estimates of the bulk water or ice specimens. The radius of a circumsphere containing about 85% of the excess electron density is treated as an effective radius of the excess electron and found to approach 2.5 A as the size of cluster increases to infinity.