Adequate representation of charge polarization effects leads to a successful treatment of the CF4+ SiCl4→ CCl4+ SiF4reaction by density functional theoryElectronic supplementary information (ESI) available: Geometries, energies of reaction, and enthalpies of reaction at 0 K. See DOI: 10.1039/c0cc02845b

Adequate polarization functions reduce the error of density functional theory (DFT) for the heat of reaction for CF4+ SiCl4from ∼9–12 kcal mol−1to ∼2–4 kcal mol−1, and using an improved density functional further reduces it to ∼1 kcal mol−1. This reaction was previously identified as a stumbling block for DFT, but we show that the problem with the previous calculations was not DFT but rather inadequate basis sets to account for intramolecular charge polarization. [ABSTRACT FROM AUTHOR]