Performance of Different Force Fields in Force Probe Simulations

Abstract

We present detailed force probe molecular dynamic simulations of mechanically interlocked dimeric calix[4]­arene–catenanes, comparing the results obtained using three different commonly used force fields (GROMOS G53a5, OPLS-AA, and AMBER GAFF). The model system is well characterized as a two-state system consisting of a closed compact and an elongated structure. Both states are stabilized by a different hydrogen-bond network, and complete separation of the dimer is prevented by the mechanical lock of the entangled aliphatic loops. The system shows fully reversible rebinding meaning that after bond rupture the system rejoins when the external force is relaxed. We present a detailed study of quantities determined in simulations using a force ramp, like the rupture force and rejoin force distributions. Additionally, we analyze the dynamics of the hydrogen-bond network. We find that the results obtained from using the different force fields qualitatively agree in the sense that always the fully reversible behavior is found. The details, like the mean rupture forces, however, do depend on the particular force field. Some of the differences observed can be traced back to differences in the strength of the hydrogen-bond networks