Clathrate hydrates recently find important practical applications in the capture and recovery of greenhouse gases, cold storage and refrigeration systems. Nevertheless, their properties at microscopic scale remains largely insufficient yet. Herein, the structure and stability of clathrate hydrates encapsulating fluorinated methane derivatives under mechanical load are investigated by molecular dynamics simulations. All investigated clathrate hydrates are structurally stable host-guest molecular crystals yet show distinct structural and mechanical behaviors. Lattice constant of those clathrate hydrates is dictated by the size and dipole moment of fluorinated methane, for example, it is initially enlarged with increasing fluorine atom in the methane guest molecule but followed by reduction as the guest molecule becomes tetrafluoromethane. However, clathrate hydrates encapsulating non-polar fluorinated methane show superior mechanical properties over those encapsulating polar ones. Polar fluorinated methane derivatives@clathrate cages exhibit distinct rotational dynamics that are influenced by strain. Moreover, all studied clathrate hydrates are mechanically failed by fractures of water cage accompanied by formation of unconventional clathrate cages. Those findings give insights into understanding the structural, thermodynamic stability and mechanical properties of clathrate hydrates encapsulating fluorinated guests.

笼形水合物最近在温室气体的捕获和回收、冷藏和制冷系统中发现了重要的实际应用。然而，它们在微观尺度上的性质仍然远远不够。在此，通过分子动力学模拟研究了包埋氟化甲烷衍生物的笼形水合物在机械载荷下的结构和稳定性。所有研究的笼形水合物都是结构稳定的主客体分子晶体，但表现出不同的结构和机械行为。这些笼形水合物的晶格常数由氟化甲烷的大小和偶极矩决定，例如，它最初随着甲烷客体分子中氟原子的增加而增大，但随后随着客体分子变成四氟甲烷而减少。然而，包封非极性氟化甲烷的笼形水合物显示出优于包封极性化合物的机械性能。极性氟化甲烷衍生物@包合物笼表现出受应变影响的独特旋转动力学。此外，所有研究过的笼形水合物均因水笼断裂而机械失效，并伴随着非常规笼形笼的形成。这些发现有助于深入了解包裹氟化客体的笼形水合物的结构、热力学稳定性和机械性能。所有研究的笼形水合物均因水笼断裂而机械失效，并伴随着非常规笼形笼的形成。这些发现有助于深入了解包裹氟化客体的笼形水合物的结构、热力学稳定性和机械性能。所有研究的笼形水合物均因水笼断裂而机械失效，并伴随着非常规笼形笼的形成。这些发现有助于深入了解包裹氟化客体的笼形水合物的结构、热力学稳定性和机械性能。