Theoretical Studies on the Intermonomer Interaction of F~-·(H_2O)_n (n = 1, 2)

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Five optimized geometries of F-?(H2O)n (n = 1, 2) were obtained with ab initio calculation at the B3LYP/6-311++G** level. The accurate intermonomer interaction energy was calculated using the MP2 electron correlation correction as well as the basis set superposition error correction by the Boys-Bernardi “counterpoise” protocol. Natural bond orbital (NBO) theory was applied to quantify the relative strength of these interactions and account for their effects on the stability, structural and vibrational parameters of Fˉ?(H2O)n (n = 1, 2). It is shown that the charge transferring from the lone pair of F-1 to the σ?OH(…F) antibonding orbital is important. The results indicate the occupancy of σ?OH(…F) is increased (denoted ?σ?OH(…F)) and the σOH(…F) bond is leng- thened (denoted ?ROH(…F)), leading to the red-shift and the red-shift values have linear correlation with both ?σ?OH(…F) and ?ROH(…F). The accurate intermonomer interaction energy was calculated using the MP2 electron correlation (n = 1, 2) was obtained with ab initio calculation at the B3LYP / 6-311 ++ G ** level. correction as well as the basis set superposition error correction by the Boys-Bernardi “counterpoise” protocol. Natural bond orbital (NBO) theory was applied to quantify the relative strength of these interactions and account for their effects on the stability, structural and vibrational parameters of Fˉ? (H2O) n (n = 1, 2). It shows that the transfer transferring from the lone pair of F-1 to the? OH (... F) antibonding orbital is important. The results indicate the occupancy of σ OH (... F) is increased (pronounced? OH? ... F)) and the? OH (... F) bond is leng-thened red-shift values ​​have linear correlation with both? σ? OH (... F) and? ROH (... F).
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