It is found from the earlier studies that the structure-dependency of totalπ-electron energyEπheavily relies on the sum of squares of the vertex degrees of the molecular graph. Hence, it provides a measure of the branching of the carbon-atom skeleton. In recent years, the sum of squares of the vertex degrees of the molecular graph has been defined as forgotten topological index which reflects the structure-dependency of totalπ-electron energyEπand measures the physical-chemical properties of molecular structures. In this paper, in order to research the structure-dependency of totalπ-electron energyEπ, we present the forgotten topological index of some important molecular structures from mathematical standpoint. The formulations we obtained here use the approach of edge set dividing, and the conclusions can be applied in physics, chemical, material, and pharmaceutical engineering.