Accurate Thermochemistry for Main-Group Elements up to Xenon with the Wn-P34 Series of Composite Methods

In the present study, we introduce the accurate Wn-P34 quantum chemistry composite methods with applicability to heavy p-block elements up to xenon. For a set of thermochemical properties for prototypical third- and fourth-row species and for a diverse set of small light-main-group species, they show accuracies of similar to 3 kJ mol(-1) or better. Overall, the Wn-P34 methods are comparable in accuracy to Wn, with a widened applicability to heavier elements. We have used Wn-P34 to compile the P34 set of accurate thermochemical values for heavy p-block species, and we have applied this set to assess a wide range of lower-cost methods. The results of our assessment show that the G4(MP2)-XK composite method provides adequate treatments for these species, but several widely used double-hybrid density functional theory (DH-DFT) methods show uncharacteristically large deviations. In contrast, we find it presently surprising that some pure and hybrid DFT methods such as TPSS and SCANh perform quite well. We hope that our findings and new tools would facilitate the application of computational chemistry for heavy elements, of which the properties are yet to be broadly explored.

Automated summary

The accurate Wn-P34 quantum chemistry composite methods introduced in this study are applicable to heavy p-block elements up to xenon, showing similar accuracies to Wn but with widened applicability to heavier elements. The G4(MP2)-XK composite method provides adequate treatments for species, while some widely used double-hybrid density functional theory methods show uncharacteristically large deviations. Surprisingly, some pure and hybrid DFT methods such as TPSS and SCANh perform quite well, facilitating the application of computational chemistry for heavy elements.