Phys Chem Chem Phys. 2022 Jun 14. doi: 10.1039/d2cp01725c. Online ahead of print.
ABSTRACT
Every practical method to solve the Schrödinger equation for interacting many-particle systems introduces approximations. Such methods are therefore plagued by systematic errors. For computational chemistry, it is decisive to quantify the specific error for some system under consideration. Traditionally, the primary way for such an error assessment has been benchmarking data, usually taken from the literature. However, their transferability to a specific molecular system, and hence, the reliability of the traditional approach always remains uncertain to some degree. In this communication, we elaborate on the shortcomings of this traditional way of static benchmarking by exploiting statistical analyses using one of the largest quantum chemical benchmark sets available. We demonstrate the uncertainty of error estimates in the light of the choice of reference data selected for a benchmark study. To alleviate the issues with static benchmarks, we advocate to rely instead on a rolling and system-focused approach for rigorously quantifying the uncertainty of a quantum chemical result.
PMID:35700515 | DOI:10.1039/d2cp01725c
