Improved model for the refractive index: application to potential components of ambient aerosol

Abstract

Understanding the impact of atmospheric aerosols on the global radiative balance requires knowing the refractive index (RI) of their components. Currently available methods to estimate this property from molecular structure are mostly empirical and exhibit significant errors (>10%). This work reports a more physically sound model leading to predictions within ±5% from experiment. The root mean square relative error is <1% for general organic compounds, and <2% for oxygen-rich compounds of special interest in aerosol chemistry. In this approach, the RI is obtained from the Lorentz–Lorenz equation. The molar volume and polarizability required as input are obtained from the addition of a so-called geometrical fragment (GF) associated with every non-hydrogen atom in the molecule. The value of this GF method to the study of ambient aerosol is demonstrated through extensive validation and application to compounds that may be present in aerosol droplets. In so doing, insight is provided into the origin of significant errors previously noted using earlier methods. Moreover, it is demonstrated that reference values of the refractive index reported in widely used compilations should be considered with caution. Finally, a Python script is provided as supplementary information for easy use of the present model to estimate molar volume and refractive index for any molecule.