High quality micro-Raman spectra of the LiClO4droplet with mass of nanogram scale were obtained at various concentrations from dilute to supersaturated state.From component band analysis of the v1-ClO4band,four peaks at 933.3,936.8,942.1 and950.7 cm 1were identified and assigned to free solvated perchlorate anion,solvent-shared ion pair,contact ion pair and complex ion aggregates,respectively.As expected,the signature of free solvated ClO4ion was observed to decrease in intensity with the increase in concentration.The intensity of the signature from solvent-shared ion pair was observed to rise with increase in concentration from 1.8 mol/kg to 5.0 mol/kg before decreasing as the concentration was further increased to 5.6mol/kg.Signatures of contact ion pair and of complex ion aggregates were shown to increase as the concentration was enhanced.Based upon the Eigen mechanism,we show that three association equilibria can be used to describe the transformations between free solvated perchlorate anion,solvent-shared ion pair,contact ion pair and complex ion aggregates.The overall association constant,K,and the stepwise association constants Ki(i=1 to 3)in the Eigen mechanism were determined separately with values of 0.025±0.003,0.023±0.002,0.068±0.033 and 0.686±0.174.Based on these constants,the electronic performance can be reasonably predicted by the optimum choice of electrolyte concentrations. High quality micro-Raman spectra of the LiClO 4 droplet with mass of nanogram scale were obtained at various concentrations from dilute to supersaturated state. From component band analysis of the v1-ClO 4 band, four peaks at 933.3, 936.8, 942.1 and 950.7 cm 1were identified and assigned to free solvated perchlorate anion, solvent-shared ion pair, contact ion pair and complex ion aggregates, respectively. As expected, the signature of free solvated ClO4ion was observed to decrease in intensity with the increase in concentration. the intensity of the signature from solvent-shared ion pair was observed to rise with increase in concentration from 1.8 mol / kg to 5.0 mol / kg before decreasing as the concentration was increased to 5.6 mol / kg. Signatures of contact ion pair and of complex ion aggregates were shown to increase as the concentration was enhanced.Based upon the Eigen mechanism, we show that three association equilibria can be used to describe the transformations between free solvated perchlo rate anion, solvent-shared ion pair, contact ion pair and complex ion aggregates. The overall association constant, K, and the stepwise association constants Ki (i = 1 to 3) in the Eigen mechanism were determined to be with separately given values ​​of 0.025 ± 0.003 , 0.023 ± 0.002, 0.068 ± 0.033 and 0.686 ± 0.174. Based on these constants, the electronic performance can be reasonably predicted by the optimum choice of electrolyte concentrations.