Considering that in our previous calculations on the reaction of bulk BMP-TFSI with Li (see Figure -f in ref. ). Li-induced N -S bond breaking was found to be highly exothermic and to proceed spontaneously with no activation barrier, and similar results were obtained also for Li-induced S -C or C -F bond breaking. Therefore, we decided to focus on these reactions also for the adsorbed monolayer. As illustrated in Table (4 th to 6 th column), these reactions are strongly exothermic also in the present case. Formation of a Li2-NSO2CF3 intermediate (N-S bond breaking) seemed to be most likely, although intermediates with broken S-C or C-F bonds are only slightly less stable and thus their formation may be possible as well (Table , 4 th to 6 th column). Finally, although not calculated explicitly for the monolayer case, we expect that similar to the reaction of Li with bulk BMP-TFSI the reaction proceeds spontaneously, with no or only a small activation barrier. For further information, we compare the calculated core level BEs of the co-adsorbed species and of the three adsorbed initial reaction products (Table ) with the experimental data. For this purpose, the calculated BEs are indicated by symbols in Figure in the top of the different panels (symbols are explained in the legend in the figure). For the F1s region, most of the adsorbed molecular species are in the range of the FTFSI+Li peak. Also the difference in BE between FTFSI+Li and FTFSI peaks is reproduced well. The products in the 5 th and 6 th row show also signals at significantly lower BE, at 686.7 eV (5 th row: S -C bond breaking) and at 685.8 eV (6 th row: C -F bond breaking), respectively, in addition to signals at higher BE.