Claude Berge (1987) introduced the concept of k-extendable graphs, wherein any independent set of size k is inherently a constituent of a maximum independent set within a graph H=(V,E). Graphs possessing the property of being 1-extendable are termedas Berge graphs. This introduction gave rise to the notion of well-covered graphs and well-dominated graphs. A graph is categorized as well-covered if each of its maximal independent sets is, in fact, a maximum independent set. Similarly, a graph attains the classification of well-dominated if every minimal dominating set (DS) within it is a minimum dominating set. In alignment with the concept of k-extendable graphs, the framework of (k,γ)-endowed graphs and symmetric (k,γ)-endowed graphs are established. In these graphs, each DS of size k encompasses a minimum DS of the graph. In this article, a study of γ-endowed dominating sets is initiated. Various results providing a deep insight into γ-endowed dominating sets in graphs such as those characterizing the ones possessing a unique minimum DS are proven. We also introduce and study the symmetric γ-endowed graphs and minimality of dominating sets in them. In addition, we give a solution to an open problem in the literature. which seeks to find a domination-based parameter that has a correlation coefficient of ρ>0.9967 with the total π-electronic energy of lower benzenoid hydrocarbons. We show that the upper dominating number Γ(H) studied in this paper delivers a strong prediction potential.