Endohedral fullerenes with a dipolar molecule enclosed in the fullerene cage have great potential in molecular electronics, such as diodes, switches, or molecular memristors. Here, we study a series of model systems based on MX@D5h(1)-C70 (M = a metal or hydrogen, X = a halogen or a chalcogen) endohedral fullerenes to identify potential molecular memristors and to derive a general formula for rapid identification of potential memristors among analogous MX@Cn systems. To obtain sufficiently accurate results for switching barriers and encapsulation energies, we perform a benchmark of ten DFT functionals against ab initio SCS-MP2 and DLPNO-CCSD(T) methods at the complete basis set limit. The whole series is then investigated using the PBE0 functional which was found to be the most efficient vs. the ab initio methods. Nine of the 34 MX@C70 molecules studied are predicted to have suitable switching barriers to be considered as potential candidates for molecular switches and memristors. We have identified several structure-property relationships for the switching barrier and response of the systems to the electric field, in particular the dependence of the switching barrier on the available space for M-X switching and faster response of the system to the electric field with a larger dipole moment of MX and MX@C70.

Faculty of Chemical Engineering University of Chemistry and Technology Prague Technická 3 CZ 16628 Prague Czech Republic

Faculty of Science Charles University Albertov 2038 6 CZ 12843 Prague Czech Republic

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nám 2 CZ 16610 Prague Czech Republic

Institute of Organic Chemistry Polish Academy of Sciences Kasprzaka 44 52 01 224 Warsaw Poland

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