QSPR STUDY ON DIRECT PHOTOLYSIS HALF-LIVES OF PAHs IN WATER SURFACE

Abstract

Quantitative structure-property relationship (QSPR) modeling is a helpful approach used to correlate the properties of pollutants with their structure descriptors. In this paper a QSPR model for direct photolysis half-lives of polycyclic aromatic hydrocarbons (PAHs) under sunlight on the water surface was developed using density functional theory (DFT) and direct photolysis half-lives of seven PAHs without reported observed values were predicted. The quantum chemical descriptors used in this study were computed at the level of B3LYP/6–311+G(d) and analyzed by partial least squares (PLS) method. The obtained QSPR model with a correlation coefficient of 0.963 was more significant than that derived from semi-empirical molecular orbital algorithm in literatures. It was found that the eigenvalues of the frontier molecular orbital (E HOMO , E LUMO , E NLUMO and E NHOMO ) are important in governing the photolysis half-lives of PAHs in water surface, while the molecular weight (MW) and molecular total energy (TE) also have great effects on photolysis half-lives. The importance of E NLUMO and E NHOMO in the model complicates the photolytic mechanism of PAHs and they might become two useful descriptors in QSPR study on photolysis.