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We study the permeation dynamics of helium and carbon dioxide through an atomistically detailed model of a polymer of intrinsic microporosity, PIM-1, via non-equilibrium molecular dynamics (NEMD) simulations. This work presents the first explicit molecular modeling of gas permeation through a high free-volume polymer sample, and it demonstrates how permeability and solubility can be obtained coherently from a single simulation. Solubilities in particular can be obtained to a very high degree of confidence and within experimental inaccuracies. Furthermore, the simulations make it possible to obtain very specific information on the diffusion dynamics of penetrant molecules and yield detailed maps of gas occupancy, which are akin to a digital tomographic scan of the polymer network. In addition to determining permeability and solubility directly from NEMD simulations, the results shed light on the permeation mechanism of the penetrant gases, suggesting that the relative openness of the microporous topology promotes the anomalous diffusion of penetrant gases, which entails a deviation from the pore hopping mechanism usually observed in gas diffusion in polymers.

Many common atomic force microscope (AFM) spring constant calibration methods regard the AFM probe as a uniform cantilever, neglecting the tip mass and any nonuniformity in the thickness of the probe along its length. This work quantifies the error in the spring constant estimated by the Sader and thermal calibration methods due to nonuniformity in the thickness of the cantilever and the influence of the mass loading effect of the probe tip. Formulae are presented that can be used to compute the uncertainty in cantilever calibration for an arbitrary thickness nonuniformity, or to correct the calibration methods if the thickness nonuniformity is known. The results show that both methods are quite sensitive to nonuniformity. When the first dynamic mode is used in the calibration, the error in the spring constant estimated by either method is between - 4% and 9% for a cantilever whose thickness increases or decreases linearly by 30% along its length. The errors are several times larger if the second or higher dynamic modes are used. To illustrate the proposed methods, a commercial AFM probe that has significant nonuniformity is considered and the error in calibrating this probe is quantified and discussed. For this particular probe, variations in the thickness of the probe over the last 15% of its length are found to significantly reduce the accuracy of the calibration when the thermal method is used, since that method is sensitive to changes in the shape of the eigenmode of the probe near its free end.

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