The evaluation or prediction of thermodynamic properties for reactive chemicals is an important concern in chemical and petrochemical industries. Typically, reactive chemicals can be evaluated using calorimetric analysis, which is both resource and time consuming. To overcome these difficulties, computational techniques are introduced as alternative solution.

This paper proposes a molecular simulation method (ab initio and DFT) to predict thermodynamic data based on molecular properties. Using the molecular simulation we can obtain new values of thermodynamics under conditions where the compounds are unstable and cannot be measured accurately or safely. Some research has been done in our group, such as predicting heat of formation for hydroxylamine (J. Phys. Chem. A 2003, 107, 1077). Examples of highly reactive and poorly characterized compounds were investigated in this work, including an unsaturated hydrocarbon, methylcyclopentadiene (MCP). In the future, this approach will be applied on energetic materials, such as 1,1-diamino-2,2-dinitroethene (FOX-7). Molecular simulation approach is a practical method to predict thermodynamic properties.