Nonempirical Description of the Atmospherically Important Anionic Species. I. Water Cluster Anions |
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Authors: | Novakovskaya Yu. V. Stepanov N. F. |
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Affiliation: | (1) Laboratory of Quantum Mechanics and Molecular Structure, Department of Chemistry, Moscow State University, Leninskie Gory, Moscow, 119234, Russia |
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Abstract: | Water cluster anions, comprising up to 20 molecules, are simulated at the second-order unrestricted Møller–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 Å as the size of cluster increases to infinity. |
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Keywords: | Water cluster anions interface structures electron density distribution electron affinity electron detachment energy |
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