Comment on 'The Water-Exchange Mechanism of the [UO2(OH2)5] + Ion Revisited:The Importance of a Proper Treatment of Electron Correlation' [F.P.Rotzinger Chem.Eur.J.,2007,13,800]

摘要

In a previous paper (page 2019 of reference [1]),Rotzinger has discussed what he refers to as static and dynamic correlation and states "In UO2(OH2)5~(2+),there is static electron correlation,arising from the population of sigma*(M=O) and pi*(M=O)s by sigma(M=O) and pi(M=O) electrons as in VO-(OH2)_5~(2+)".In that paper,Rotzinger did not study the ura-nyl(VI) aqua ion and his statements in reference [1] are therefore not supported by any computations.His claim that quantum-chemical calculations describing the structure of uranyl complexes and their dynamics using wave function based methods at the MP2 levels are flawed due to neglect of static correlation is erroneous as we have pointed out in a previous publication.In a recent paper'31 Rotzinger has found it expedient to base his previous claim on computational evidence and we applaud this.Despite considerable computational efforts his conclusions are still flawed;his own calculations (and some additional ones made by us) demonstrate very clearly that it is entirely proper to use the MP2 method in computational studies of the uranyl(VI) ion.