Quantum Chemical Calculation and Evaluation of Partition Coefficients for Classical and Emerging Environmentally...

Octanol/water (K_OW), octanol/air (K_OA), and hexadecane/air (K_HdA) partition coefficients are calculated for 67 organic compounds of environmental concern using computational chemistry. The extended CRENSO workflow applied here includes the calculation of extensive conformer ensembles with semiempirical methods and refinement through density functional theory, taking into account solvation models, especially COSMO-RS, and thermostatistical contributions. This approach is particularly advantageous for describing large and nonrigid molecules. With regard to K_OW and K_HdA, one can refer to many experimental data from direct and indirect measurement methods, and very good matches with results from our quantum chemical workflow are evident. In the case of the K_OA values, however, good matches are only obtained for the experimentally determined values. Larger systematic deviations between data computed here and available, nonexperimental quantitative structure-activity relationship literature data occur in particular for phthalic acid esters and organophosphate esters. From a critical analysis of the coefficients calculated in this work and comparison with available literature data, we conclude that the presented quantum chemical composite approach is the most powerful so far for calculating reliable partition coefficients because all physical contributions to the conformational free energy are considered and the structure ensembles for the two phases are generated independently and consistently.