The EnS demonstrated the most substantial enhancement, showing significant improvement from the first optimization step and maintaining consistent performance thereafter (Figure ). This improvement is particularly evident in the PES descriptions for both CCR-IRC and CCR-SC datasets (Figures and). The final optimized parameters (step 9, black curves) achieved excellent agreement with reference M06-2X-D3/def2-TZVP calculations (red curves), with deviations predominantly under 1.0 kcal/mol for the CCR-IRC dataset. This represents a significant improvement over the original parametrization (blue curves). Notably, even the first optimization step produced PES profiles that qualitatively matched the HL reference, demonstrating the method's utility for rapid preliminary parametrization.