Molecular Dynamics-Based Modeling of Ion-Neutral Collisions in an Open Ion Trajectory Simulation Framework.

Ion mobility spectrometry (IMS) and ion mobility mass spectrometry (IMS-MS) methods have become increasingly popular and are important analytical techniques to determine information about the structural parameters of gas-phase analytes. The accurate description of the interaction between molecular ions and neutral background gas particles is an essential part of high-quality simulations of such modern mass- and ion-mobility-spectrometric systems. Established ion-neutral collision models (Hard-sphere collision modeling and statistical diffusion simulations) in common ion-trajectory simulation systems like SIMION use strongly simplified assumptions and are thus limited in their predictive ability. In contrast, collision cross-section (CCS) modeling programs (e.g., MOBCAL, IMoS, and Colloidoscope) allow high-quality ion mobility predictions for low-field equilibrium conditions using explicit scattering processes with a molecular dynamics-based trajectory method but cannot be used for nonequilibrium collision modeling in an ion trajectory simulation. This work presents an extension to the open-source Ion Dynamics Simulation Framework (IDSimF), which allows the simulation of ion dynamics under arbitrary and even nonequilibrium conditions. It was extended by an advanced collision model employing the molecular dynamics trajectory method for a detailed microscopic description of ion-neutral collisions within ion-trajectory simulations. We used drift tube ion mobility spectrometry (DT-IMS) to validate the predictive abilities of the model and to estimate the runtime requirements for productive simulations. Simulated high-field ion mobilities for small ion systems in a drift tube IMS are compared to experimental values from the literature and an implementation of a hard-sphere model in IDSimF for helium and argon as background gas particles. Significant improvements in ion mobility predictions using the molecular dynamics trajectory approach are obtained with deviations of only a few percent from experimental values. Therefore, the established and publicly available MD collision model will serve as foundation for nonequilibrium ion dynamics simulations and the development of improved ion dynamics modeling methods.