The Limited Predictive Power of the Pauling Rules

The Pauling rules have served to analyze and rationalize crystal structures for decades. So far, there is no statistical answer on how these five rules perform. Here, we show the analysis of all five Pauling rules based on the geometrical data of around 5000 oxides. To do this, we determined the coordination environments of all 5000 oxides and compared our geometrical analysis to the prediction of the Pauling rules. We arrived at the conclusion that the Pauling rules - especially the electrostatic valence principle - perform poorly for most of the oxides: only 13% of all oxides simultaneously satisfy rules from two to five. To arrive at such an intuitive understanding of the stability of crystals that Pauling’s rules gave shortly after their development again, we should develop new and improved rules.