Evaluation of static differential capacitance at the [C4mim+][TFSA-]/electrode interface using molecular dynamics simulation combined with electrochemical surface plasmon resonance measurements

Molecular dynamic (MD) simulations have been performed for 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C(4)mim(+)][TFSA(-)]), an ionic liquid (IL), on a charged graphene electrode to achieve the quantitative analysis of the static differential capacitance using the electrochemical surface plasmon resonance (ESPR). The MD simulations have provided the surface charge density on the electrode and ionic distributions in the electric double layer, both of which are indispensable for the evaluation of static differential capacitance using ESPR but are difficult to be measured by experimental techniques. This approach has allowed the quantitative analysis and explanation of the SPR angle shift in ESPR. The major contribution to the SPR angle shift is found to be the change in ionic concentrations of the first ionic layer on the electrode, owing to higher polarizabilities of ions in the first ionic layer than those in the overlayers. Moreover, the ionic orientation on the electrode and ionic multilayer structure have also been investigated in detail. The butyl group of C(4)mim(+) in the first ionic layer is found to provide extra room for C(4)mim(+) in the second ionic layer but exclude TFSA(-), which affects the interval and regularity of ionic multilayers.

Automated summary

Molecular dynamic simulations were conducted on a charged graphene electrode with the ionic liquid [C(4)mim(+)][TFSA(-)] to analyze static differential capacitance, providing insights into the surface charge density, ionic distributions, and ionic orientation essential for understanding SPR angle shifts in ESPR. The simulations revealed that changes in ionic concentrations of the first ionic layer play a key role in the SPR angle shift, highlighting the importance of ion distributions and orientations in the evaluation of ESPR.