Explaining and Fixing DFT Failures for Torsional Barriers

Abstract

Most torsional barriers are predicted to high accuracy (about 1 kJ/mol) by standard semilocal functionals, but a small subset has been found to have much larger errors. We create a database of almost 300 carbon-carbon torsional barriers, including 12 poorly behaved barriers, all stemming from Y=C-X group, where X is O or S, and Y is a halide. Functionals with enhanced exchange mixing (about 50%) work well for all barriers. We find that poor actors have delocalization errors caused by hyperconjugation. These problematic calculations are density sensitive (i.e., DFT predictions change noticeably with the density), and using HF densities (HF-DFT) fixes these issues. For example, conventional B3LYP performs as accurately as exchange-enhanced functionals if the HF density is used. For long-chain conjugated molecules, HF-DFT can be much better than exchange-enhanced functionals. We suggest that HF-PBE0 has the best overall performance.