The remaing 32 states have a Rydberg character. Table illustrates that for the thiophene molecule, the 1𝐴 2 and 2𝐴 2 states look strongly mixed with the 6-31+G(d) whereas the situation is clearer with larger basis sets. Indeed the values are: 110.9 a.u. (1𝐴 2 ), and 11.5 a.u. (2𝐴 2 ) with aug-cc-pVTZ, whilw 115.8 a.u. (1𝐴 2 ), and 9.8 a.u. (2𝐴 2 ) with aug-cc-pVDZ. The Q-CC3/6-31+G(d) method is enable to distinguish these two states, separated by 0.06 eV only, resulting in a splitting of the 𝛿 TPA values (68.3 and 44.7 a.u.). As previously stated we consequently summed these two contributions and considered them as a single state in this case.