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Scheduling large-scale applications on the Grid is a fundamental challenge and is critical to application performance and cost. Large-scale applications typically contain a large number of homogeneous and concurrent activities which are main bottlenecks, but open great potentials for optimization. This paper presents a new formulation of the well-known NP-complete problems and two novel algorithms that addresses the problems. The optimization problems are formulated as sequential cooperative games among workflow managers. Experimental results indicate that we have successfully devised and implemented one group of effective, efficient, and feasible approaches. They can produce soultuins of significantly better performance and cost than traditional algorithms. Our algorithms have considerably low time complexity and can assign 1,000,000 activities to 10,000 processors within 0.4 second on one Opteron processor. Moreover, the solutions can be practically performed by workflow managers, and the violation of QoS can be easily detected, which are critical to fault tolerance.