Optical nanoantennas, just like their radio-frequency equivalents, enhance the light-matter interaction in their feed gap. Antenna enhancement of small signals promises to open a new regime in linear and nonlinear spectroscopy on the nanoscale. Without antennas especially the nonlinear spectroscopy of single nanoobjects is very demanding. Here we present the first antenna-enhanced ultrafast nonlinear optical spectroscopy. In particular, we use the antenna to determine the nonlinear transient absorption signal of a single gold nanoparticle caused by mechanical breathing oscillations. We increase the signal amplitu-de by an order of magnitude, which is in good agreement with our analytical and numerical models. Our method will find applications in linear and nonlinear spectroscopy of single nanoobjects, especially in simplifying such challenging experiments as transient absorption or multiphoton excitation.

We report simulations on the homogeneous liquid-fcc nucleation of charged colloids for both low and high contact energy values. As a precursor for crystal formation, we observe increased local order at the position where the crystal will form, but no correlations with the local density. Thus, the nucleation is driven by order fluctuations rather than density fluctuations. Our results also show that the transition involves two stages in both cases, first a transition of liquid → bcc, followed by a bcc → hcp/fcc transition. Both transitions have to overcome free energy barriers, so that a spherical bcc-like cluster is formed first, in which the final fcc structure is nucleated mainly at the surface of the crystallite. This means that the second stage bcc-fcc phase transition is a heterogeneous nucleation in the partially grown solid phase, even though we start from a homogeneous bulk liquid. The height of the bcc → hcp/fcc free energy barrier strongly depends on the contact energies of the colloids. For low contact energy this barrier is low, so that the bcc → hcp/fcc transition occurs spontaneously. For the higher contact energy, the second barrier is too high to be crossed spontaneously by the colloidal system. However, it was possible to ratchet the system over the second barrier and to transform the bcc nuclei into the stable hcp/fcc phase. The transitions are dominated by the first liquid-bcc transition and can be described by classical nucleation theory using an effective surface tension.

Forward flux sampling (FFS) provides a convenient and efficient way to simulate rare events in equilibrium or non-equilibrium systems. FFS ratchets the system from an initial state to a final state via a series of interfaces in phase space. The efficiency of FFS depends sensitively on the positions of the interfaces. We present two alternative methods for placing interfaces automatically and adaptively in their optimal locations, on-the-fly as an FFS simulation progresses, without prior knowledge or user intervention. These methods allow the FFS simulation to advance efficiently through bottlenecks in phase space by placing more interfaces where the probability of advancement is lower. The methods are demonstrated both for a single-particle test problem and for the crystallization of Yukawa particles. By removing the need for manual interface placement, our methods both facilitate the setting up of FFS simulations and improve their performance, especially for rare events which involve complex trajectories through phase space, with many bottlenecks.

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