Valence electronic structure of [EMIM][B(CN)4]: Ion-pair vs. bulk description




I. Kuusik, M. Berholts, J. Kruusma, A. Tõnisoo, E. Lust, E. Nõmmiste, V. Kisanda

PublisherRoyal Society of Chemistry

2019

RSC Advances

RSC Advances

9

57

33140

33146

7

2046-2069

2046-2069

DOIhttps://doi.org/10.1039/c9ra06762k

https://research.utu.fi/converis/portal/detail/Publication/43732673



The ultraviolet photoelectron spectrum of the [EMIM][B(CN)4] ionic liquid was recorded and analyzed. Together with different ab initio calculation methods, detailed insight into the electronic structure of this simple room temperature ionic liquid is possible. The ion-pair approximation to the liquid electronic structure was not sufficient. Therefore bulk ab initio calculations were performed on a proposed crystal structure. The modelling of bulk electronic spectra is able to explain the experimental electronic structure of the ionic liquid. Most notably, the dispersion corrected PBE calculation (PBE-D3BJ) showed good agreement with the experimental UPS spectrum. The spectra simulated by the B97-D and the BLYP-D3(BJ) functionals were also in agreement with the experimental data. The LDA approximation only provided qualitative agreement while the optB88-vdW and CX-vdW functionals were not good. However, it will be shown that many requirements have to be met in order to accurately describe the electronic structure of this ionic liquid.


Last updated on 2024-26-11 at 19:29