Insight into organic reactions from the direct random phase approximation and its corrections

Adrienn Ruzsinszky, Igor Ying Zhang, Matthias Scheffler
2015 Journal of Chemical Physics  
The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The
more » ... ond test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges. C 2015 AIP Publishing LLC. [http://dx.
doi:10.1063/1.4932306 pmid:26472371 fatcat:eb6u24hudfcwpnqkl4yrq4wrcu