Atom-by-atom engineering of nanomaterials requires atomic-level knowledge of the size evolution mechanism of nanoparticles, which remains one of the greatest mysteries in nanochemistry. Here we reveal atomic-level dynamics of size evolution reaction of molecular-like nanoparticles, i.e., nanoclusters (NCs) by delicate mass spectrometry (MS) analyses. The model size-conversion reaction is [Au23(SR)16]− → [Au25(SR)18]− (SR = thiolate ligand). We demonstrate that such isoelectronic (valence electron count is 8 in both NCs) size-conversion occurs by a surface-motif-exchange-induced symmetry-breaking core structure transformation mechanism, surfacing as a definitive reaction of [Au23(SR)16]− + 2 [Au2(SR)3]− → [Au25(SR)18]− + 2 [Au(SR)2]−. The detailed tandem MS analyses further suggest the bond susceptibility hierarchies in feed and final Au NCs, shedding mechanistic light on cluster reaction dynamics at atomic level. The MS-based mechanistic approach developed in this study also opens a complementary avenue to X-ray crystallography to reveal size evolution kinetics and dynamics.

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Entrainment rate is a critical but highly uncertain quantity in convective parameterizations; especially, the effects of environmental relative humidity on entrainment rate are controversial, or even opposite, in different studies. Analysis of aircraft observations of cumuli from the Routine AAF (Atmospheric Radiation Measurement [ARM] Aerial Facility) Clouds with Low Optical Water Depths (CLOWD) Optical Radiative Observations (RACORO) and Rain in Cumulus over the Ocean (RICO) field campaigns shows that entrainment rate is positively correlated with relative humidity. Physical analysis shows that higher relative humidity promotes entrainment by reducing buoyancy in the cloud cores and by weakening downdrafts near the cloud cores. The reduced buoyancy in the cloud cores and weakened downdrafts surrounding the cores further reduce updrafts in the cloud cores; the cloud cores with smaller updrafts are more significantly affected by their environment, resulting in larger entrainment rate. The relationship between entrainment rate and relative humidity is consistent with the buoyancy sorting concept widely used in convection parameterizations. The results provide reliable in situ observations to improve parameterizations of entrainment rate.

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Unidirectional pedestrian movement is a special phenomenon in the evacuation process of large public buildings and urban environments at pedestrian scale. Several macroscopic models for collective behaviors have been built to predict pedestrian flow. However, current models do not explain the diffusion behavior in pedestrian crowd movement, which can be important in representing spatial-temporal crowd density differentiation in the movement process. This study builds a macroscopic model for describing crowd diffusion behavior and evaluating unidirectional pedestrian flow. The proposed model employs discretization of time and walking speed in geometric distribution to calculate downstream pedestrian crowd flow and analyze movement process based on upstream number of pedestrians and average walking speed. The simulated results are calibrated with video observation data in a baseball stadium to verify the model precision. Statistical results have verified that the proposed pedestrian diffusion model could accurately describe pedestrian macromovement behavior within the margin of error.

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