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| - Binding Energies and Structures of NaI−(CH3CN)n=1-9 Clusters: Theoretical Study of theContact Ion Pair versus the Solvent-Separated Ion Pair Structures in a Molecular Cluster
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| - We present a theoretical study of the charge separation of NaI clustered with acetonitrile molecules. A modelpotential specially devised for the NaI−(CH3CN)n system has been built up according to the exchangeperturbation theory as developed by Claverie. The potential energy surface (PES) exploration has been carriedout using the Monte Carlo growth method (MCGM) at different fixed internuclear NaI distances, to obtaina minimum energy profile for the NaI bond breaking. From four to nine solvent molecules, the NaI−(CH3CN)n PES exhibits two local minima along the NaI internuclear distance. The first one is related to the contaction pair (CIP) structure and the second where the two ions are separated by two or three acetonitrile moleculesin a solvent-separated ion pair (SSIP) structure. With less than eight solvent molecules, the CIP configurationshave the highest binding energies, but for nine acetonitrile molecules, the configurations where the two ionsare separated by 7 Å have a higher binding energy than those where the two ions stay in contact (2.85 Å),reflecting an evolution from the CIP to the SSIP structures with the cluster size. This can be related to arecent gas phase photoionization experiment on NaI−(CH3CN)n and leads to the same conclusion: the chargeseparation of NaI should be achieved within a cluster containing fewer than 10 acetonitrile molecules.
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