Ab initio and density functional theory studies for the explanation of the antioxidant activity of certain phenolic acids

Ab initio and density functional theory molecular orbital calculations were carried out at both the HF/6‐31+G(d) and B3LYP/6‐31+G(d) levels for the four antioxidants, p‐hydroxycinnamic acid derivatives, namely, the p‐coumaric, caffeic, ferulic, and sinapinic acid and the corresponding radicals, in an attempt to explain the structural dependency of the antioxidant activity of these compounds. Optimized resulting geometries, vibrational frequencies, absolute infrared intensities, and electron‐donating ability are discussed. Both the high degree of conjugation and the extended spin delocalization in the phenoxyl radicals offer explanation for the scavenging activity of the four acids. In structurally related compounds, the calculated heat of formation value in radical formation appears as a meaningful molecular descriptor of antioxidant activity in accordance with experimental data. This becomes more clear at the B3LYP level.