Truck platooning enables a group of trucks to move close together, which helps reduce truck fuel use and increase effective road capacity. In this paper, a system-level equilibrium model is developed to characterize spontaneous truck platooning with coexistence of non-platooning vehicles in a network, by explicitly accounting for the interlocking relationship among platoon formation time, truck fuel saving, and increase in effective road capacity. To equilibrate the relationships, an algorithm is proposed which involves a diagonalization approach and a bush based algorithm to solve decomposed subproblems. The condition of proportionality is imposed to obtain unique traffic flows for each class of vehicles on road links. In addition, a spatially constrained multivariate clustering technique is employed to construct origin/destination zones that are smaller than the coarse Freight Analysis Framework (FAF) zones, while maintaining reasonable computational burden for network traffic assignment. Model implementation in the U.S. shows that platooning could lead to 7.9% fuel saving among platoonable trucks in 2025 and a comparable increase in effective capacity of platoonable road links, which would account for 60% of rural interstate roads. The fuel saving and road capacity improvement translate into an annual cost reduction of $\$$868 million for the U.S. intercity trucking sector and reduced road infrastructure investment needs worth $\$$4.8 billion. Extensive sensitivity analysis further reveals that fuel saving of platoonable trucks increases with platoon size but decreases with inter-truck distance in a platoon. Fuel saving potential suggests that priority should be given to rural rather than urban roads in deploying platooning technologies. As we expected, greater market penetration of platooning technologies means higher fuel saving and greater increase in effective road capacity.