- Amin Alibakhshi Theoretical Chemistry, Institute for Physical Chemistry, Christian-Albrechts-University
Accurate evaluation of combustion enthalpy is of high scientific and industrial importance. Although via ab-initio computation of heat of reactions, as one of the promising and well-established approaches in computational chemistry, this goal should in principle be achievable, examples of reliable and precise evaluation of heat of combustion by ab-initio methods has surprisingly not yet been reported. A handful of works carried out for this purpose report significant inconsistencies between the ab-initio evaluated and experimentally determined combustion enthalpies and suggest empirical corrections to improve the accuracy of predicted data. With this background, the main aims of the present study is to investigate the reasons behind those reported inconsistencies and propose guidelines for highly accurate evaluation of combustion enthalpy via ab-initio computations. Through the provided guidelines, the most accurate results ever reported, with average absolute deviation, mean unsigned error and correlation coefficient of 1.556 kJ/mole, 0.072% and 0.99999, respectively, is achieved for theoretically computed combustion enthalpies of 40 studied hydrocarbons.