Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics.

Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved. Here, we adopt our newly developed Trajectory Surface Hopping (TSH) nonadiabatic molecular dynamics algorithm to simulate plasmon relaxation in Au20 clusters, taking the atomistic details into account. The electronic properties are treated within the Linear Response Time-Dependent Tight-binding Density Functional Theory (LR-TDDFTB) framework. The relaxation of plasmon due to coupling to phonon modes in Au20 beyond the Born-Oppenheimer approximation is described by the TSH algorithm. The numerically efficient LR-TDDFTB method allows us to address a dense manifold of excited states to ensure the inclusion of plasmon excitation. Starting from the photoexcited plasmon states in Au20 cluster, we find that the time constant for relaxation from plasmon excited states to the lowest excited states is about 2.7 ps, mainly resulting from a stepwise decay process caused by low-frequency phonons of the Au20 cluster. Furthermore, our simulations show that the lifetime of the phonon-induced plasmon dephasing process is ∼10.4 fs and that such a swift process can be attributed to the strong nonadiabatic effect in small clusters. Our simulations demonstrate a detailed description of the dynamic processes in nanoclusters, including plasmon excitation, hot carrier generation from plasmon excitation dephasing, and the subsequent phonon-induced relaxation process.

The responsive behaviors of bilayer membrane under uniaxial mechanical probe.

In experiments, atomic force microscopy technology was used to measure the modulus of the membrane. However, these studies mainly focus on the linear responsive behavior. In the present work, a theoretical study is performed to show the nonlinear responsive behavior, which includes the stretching induced structural transitions. It demonstrates that the structural transition of the bilayer membrane takes place during the stretching process of the mechanical probe. A vertical cylindrical micelle can be obtained by stretching the membrane under deep compression conditions, and the cylindrical micelle can grow continuously along the axial direction. Moreover, under shallow compression conditions, the probe pulls a spherical micelle from the membrane, and then, the membrane returns to flatness. A comprehensive study is performed to show the mechanism of the responsive behaviors of the structural transition during the compression and stretching processes. When the probe acts on the B-rich layer, it is more likely to pull out a regular micelle. However, when the probe acts on the bottom A-rich layer, complex vesicles are more likely to be pulled out from the bilayer membrane. This study provides a comprehensive diagram of the mechanical responsive behavior of the membrane, which would be a guide for an experiment of biomembranes and the design of new self-assembled structures.