title: In Silico Calculation of Infinite Dilution Activity Coefficients of Molecular Solutes in Ionic Liquids: Critical Review of Current Methods and New Models Based on Three Machine Learning Algorithms.
abstract: The aim of the paper is to address all the disadvantages of currently available models for calculating infinite dilution activity coefficients (γ(∞)) of molecular solutes in ionic liquids (ILs)-a relevant property from the point of view of many applications of ILs, particularly in separations. Three new models are proposed, each of them based on distinct machine learning algorithm: stepwise multiple linear regression (SWMLR), feed-forward artificial neural network (FFANN), and least-squares support vector machine (LSSVM). The models were established based on the most comprehensive γ(∞) data bank reported so far (>34 000 data points for 188 ILs and 128 solutes). Following the paper published previously [J. Chem. Inf. Model 2014, 54, 1311-1324], the ILs were treated in terms of group contributions, whereas the Abraham solvation parameters were used to quantify an impact of solute structure. Temperature is also included in the input data of the models so that they can be utilized to obtain temperature-dependent data and thus related thermodynamic functions. Both internal and external validation techniques were applied to assess the statistical significance and explanatory power of the final correlations. A comparative study of the overall performance of the investigated SWMLR/FFANN/LSSVM approaches is presented in terms of root-mean-square error and average absolute relative deviation between calculated and experimental γ(∞), evaluated for different families of ILs and solutes, as well as between calculated and experimental infinite dilution selectivity for separation problems benzene from n-hexane and thiophene from n-heptane. LSSVM is shown to be a method with the lowest values of both training and generalization errors. It is finally demonstrated that the established models exhibit an improved accuracy compared to the state-of-the-art model, namely, temperature-dependent group contribution linear solvation energy relationship, published in 2011 [J. Chem. Eng. Data 2011, 56, 3598-3606].
authors.affiliation: Department of Physical Chemistry, Faculty of Chemistry Warsaw University of Technology , Noakowskiego 3, 00-664 Warsaw, Poland.
authors.forename: Kamil
authors.initials: K
authors.lastname: Paduszyński
mesh_terms: D003198:Computer Simulation; D052578:Ionic Liquids / Q000737:chemistry*; D016014:Linear Models; D000069550:Machine Learning; D008958:Models, Molecular; D008968:Molecular Conformation; D016571:Neural Networks, Computer; D012996:Solutions; D060388:Support Vector Machine
chemical_list: D052578:Ionic Liquids; D012996:Solutions