title: Accurate prediction of enthalpies of formation for a large set of organic compounds.
abstract: This article describes a multiparameter calibration model, which improves the accuracy of density functional theory (DFT) for the prediction of standard enthalpies of formation for a large set of organic compounds. The model applies atom based, bond based, electronic, and radical environmental correction terms to calibrate the calculated enthalpies of formation at B3LYP/6-31G(d,p) level by a least-square method. A diverse data set of 771 closed-shell compounds and radicals is used to train the model. The leave-one-out cross validation squared correlation coefficient q(2) of 0.84 and squared correlation coefficient r(2) of 0.86 for the final model are obtained. The mean absolute error in enthalpies of formation for the dataset is reduced from 4.9 kcal/mol before calibration to 2.1 kcal/mol after calibration. Five-fold cross validation is also used to estimate the performance of the calibration model and similar results are obtained.
authors.affiliation: College of Chemistry, Sichuan University, Chengdu 610065, People's Republic of China.
authors.forename: Cun-Xi
authors.initials: CX
authors.lastname: Liu
authors.forename: Hai-Xia
authors.initials: HX
authors.lastname: Wang
authors.forename: Ze-Rong
authors.initials: ZR
authors.lastname: Li
authors.forename: Chong-Wen
authors.initials: CW
authors.lastname: Zhou
authors.forename: Han-Bing
authors.initials: HB
authors.lastname: Rao
authors.forename: Xiang-Yuan
authors.initials: XY
authors.lastname: Li
mesh_terms: D002138:Calibration; D016018:Least-Squares Analysis; D056004:Molecular Dynamics Simulation; D009930:Organic Chemicals / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D009930:Organic Chemicals