The Limited Predictive Power of the Pauling Rules.

Area of Science:

• Crystallography
• Inorganic Chemistry
• Materials Science

Background:

• Pauling's rules are foundational empirical guidelines for rationalizing ionic crystal structures.
• Despite their widespread use, a comprehensive statistical evaluation of their predictive performance has been lacking.

Purpose of the Study:

• To statistically assess the performance of all five Pauling rules.
• To determine the predictive power of Pauling's rules for a large dataset of known oxides.

Main Methods:

• A rigorous and automated testing methodology was applied.
• The study analyzed a dataset comprising approximately 5000 known oxide compounds.

Main Results:

• Each of the five Pauling rules was individually evaluated.
• The analysis highlighted the limitations and specific ranges of applicability for each rule concerning chemical compositions and structural types.
• Only 13% of the studied oxides simultaneously satisfied the last four Pauling rules.

Conclusions:

• The predictive power of Pauling's rules for ionic oxides is significantly lower than commonly assumed.
• The findings underscore the need for refined or alternative approaches for crystal structure prediction in inorganic chemistry.