Proton affinities of H2O for 4 levels of theory calculated via formula (*) in the tutorial (all values in kcal/mol) ******************************************************************* level of theory /\E(ele) /\ZPE P(A) ------------------------------------------------------------------- HF/6-31G -182.60 8.74 175.34 ------------------------------------------------------------------- HF/TZV -176.71 8.61 169.58 ------------------------------------------------------------------- CCSD(T)//HF/6-31G -182.93 8.74 175.67 ------------------------------------------------------------------- CCSD(T)//HF/TZV -175.65 8.61 168.51 ------------------------------------------------------------------- Computation of corrections C1 and C2 (in kcal/mol) ******************************************************************* C1 = 169.58 - 175.34 = -5.76 C2 = 175.67 - 175.34 = 0.32 Hence we can estimate P(H20,CCSD(T)//HF/TZV) to be P = P(H20,HF/6-31G) + C1 + C2 = 175.34 - 5.76 + 0.32 = 169.90 which has to be compared with the "true" value of P(H20,CCSD(T)//HF/TZV) = 168.51 and is therefore in good agreement!