Statistical Equivalence of Quantum Chemical Methods for Energy Distribution in Water Clusters

Abstract

AbstractMethods of quantum chemistry are instrumental in understanding molecular structures and properties. However, the results demonstrate significant variability, which is difficult to predict and rationalize. The fundamental question is whether some molecular systems exhibit properties invariant with respect to the computational method. The idea explored here is that collective properties of statistical ensembles should be more robust than characteristics of individual molecules and their arbitrary sets. This effect is demonstrated for the complete set of hydrogen‐bond topologies of the dodecahedral water cluster (H2O)20. Non‐Gaussian energy distributions produced by various methods have the same functional form despite strong differences in mean values and standard deviations. The conclusion is tested on methods of different complexity and origin employing a number of criteria. A linear mapping between the energies produced by different methods is discussed. The significance of the results is in establishing a collective equivalence property of quantum chemical methods.