Lithium, sodium, and potassium cation basicities were calculated for some Lewis bases using the DFT B3LYP/6-311+G**, G2, G2(MP2), G3, and CBS-QB3 methods and compared with corresponding experimental values. The best results for lithium cation basicities (LCB) were obtained with the G2, G2(MP2), and CBS-QB3 methods. So, the G2(MP2) method seems to be the best compromise between speed and accuracy for the calculations of LCBs. Also the quicker DFT B3LYP/6-311+G** level of theory can be used for quantitative prediction of LCBs, if the systematic error is taken into account. For sodium cation basicities (SCB) both G2 and G2(MP2) methods gave excellent correlation and mean absolute deviation (0.6–0.7 kcal/mol), thus G2(MP2) can be suggested for calculation of SCB. The less expensive DFT B3LYP/6-311+G** method gave also good correlation with the experiment. Potassium cation affinities can be calculated with equal accuracy using three methods: G2, G2(MP2), and B3LYP/6-311+G**.
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