Tackling an accurate description of molecular reactivity with double-hybrid density functionals

In this Communication, we assess a panel of 18 double-hybrid density functionals for the modeling of the thermochemical and kinetic properties of an extended dataset of 449 organic chemistry reactions belonging to the BH9 database. We show that most of DHs provide a statistically robust performance to model barrier height and reaction energies in reaching the chemical accuracy. In particular, we show that nonempirical DHs, such as PBE0-DH and PBE-QIDH, or minimally parameterized alternatives, such as omega B2PLYP and B2K-PLYP, succeed to accurately model both properties in a balanced fashion. We demonstrate, however, that parameterized approaches, such as omega B97X-2 or DSD-like DHs, are more biased to only one of both properties. Published under an exclusive license by AIP Publishing.

Automated summary

In this study, we evaluate the performance of 18 double-hybrid density functionals in modeling the thermochemical and kinetic properties of 449 organic chemistry reactions. We find that most of the double-hybrid functionals provide statistically robust results in modeling barrier height and reaction energies to chemical accuracy. Nonempirical and minimally parameterized double-hybrid functionals show balanced accuracy in modeling both properties, while parameterized approaches tend to be biased towards only one of the properties.