Dipole moments of trans- and cis-(4-methylcyclohexyl)methanol (4-MCHM): obtaining the right conformer for the right reason.

Accurate computational estimates of fundamental physical properties can be used as inputs in the myriad of extant models employed to predict toxicity, transport, and fate of contaminants. However, as molecular complexity of contaminants increases, it becomes increasingly difficult to determine the magnitude of the errors introduced by ignoring the 3D conformational space averaging within group-additivity and semi-empirical approaches. The importance of considering 3D molecular structure is exemplified for the dipole moments of cis and trans isomers of (4-methylcyclohexyl)methanol (4-MCHM). When 10 000 gallons of 4-MCHM was spilled into the Elk River in January 2014, a lack of toxicological data and environmental partitioning coefficients hindered the immediate protection of human health and the local water supply in West Virginia, USA. Post-spill analysis of the contaminants suggested that the cis and trans isomers had observably different partitioning coefficients and solubility, and thus differing environmental fates. Obtaining high-quality dipole moments using ab initio quantum chemical methods for the isomeric pair was crucial in validating their experimental differences in solubility [Environ. Sci. Technol. Lett., 2015, 2, 127]. The use of first principles electronic structure theory is further explored here to obtain accurate conformer relative energies and dipole moments of cis- and trans-4-MCHM. Overall, the MP2 aug-cc-pVDZ level of theory affords the best balance between accuracy and computational cost.