Efficient Generation of Two-Photon Excited Phosphorescence from Molecules in Plasmonic Nanocavities.

Nonlinear molecular interactions with optical fields produce intriguing optical phenomena and applications ranging from color generation to biomedical imaging and sensing. The nonlinear cross-section of dielectric materials is low and therefore for effective utilisation, the optical fields need to be amplified. Here, we demonstrate that two-photon absorption can be enhanced by 108 inside individual plasmonic nanocavities containing emitters sandwiched between a gold nanoparticle and a gold film. This enhancement results from the high field strengths confined in the nanogap, thus enhancing nonlinear interactions with the emitters. We further investigate the parameters that determine the enhancement including the cavity spectral position and excitation wavelength. Moreover, the Purcell effect drastically reduces the emission lifetime from 520 ns to <200 ps, turning inefficient phosphorescent emitters into an ultrafast light source. Our results provide an understanding of enhanced two-photon-excited emission, allowing for optimization of efficient nonlinear light-matter interactions at the nanoscale

Accelerated Molecular Vibrational Decay and Suppressed Electronic Nonlinearities in Plasmonic Cavities through Coherent Raman Scattering

Molecular vibrations and their dynamics are of outstanding importance for electronic and thermal transport in nanoscale devices as well as for molecular catalysis. The vibrational dynamics of <100 molecules are studied through three-colour time-resolved coherent anti-Stokes Raman spectroscopy (trCARS) using plasmonic nanoantennas. This isolates molecular signals from four-wave mixing (FWM), while using exceptionally low nanowatt powers to avoid molecular damage via single-photon lock-in detection. FWM is found to be strongly suppressed in nm-wide plasmonic gaps compared to plasmonic nanoparticles. The ultrafast vibrational decay rates of biphenyl-4-thiol molecules are accelerated ten-fold by a transient rise in local non-equilibrium temperature excited by enhanced, pulsed optical fields within these plasmonic nanocavities. Separating the contributions of vibrational population decay and dephasing carefully explores the vibrational decay channels of these tightly confined molecules. Such extreme plasmonic enhancement within nanogaps opens up prospects for measuring single-molecule vibrationally-coupled dynamics and diverse molecular optomechanics phenomena

Nanoscopy through a plasmonic nanolens.

Plasmonics now delivers sensors capable of detecting single molecules. The emission enhancements and nanometer-scale optical confinement achieved by these metallic nanostructures vastly increase spectroscopic sensitivity, enabling real-time tracking. However, the interaction of light with such nanostructures typically loses all information about the spatial location of molecules within a plasmonic hot spot. Here, we show that ultrathin plasmonic nanogaps support complete mode sets which strongly influence the far-field emission patterns of embedded emitters and allow the reconstruction of dipole positions with 1-nm precision. Emitters in different locations radiate spots, rings, and askew halo images, arising from interference of 2 radiating antenna modes differently coupling light out of the nanogap, highlighting the imaging potential of these plasmonic "crystal balls." Emitters at the center are now found to live indefinitely, because they radiate so rapidly.We acknowledge EPSRC grants EP/N016920/1, EP/L027151/1, and NanoDTC EP/L015978/1. OSO acknowledges support of Rubicon fellowship from the Netherlands Organisation for Scientific Research, and RC thanks support from Trinity College Cambridge

A Search for Variability in Exoplanet Analogues and Low-Gravity Brown Dwarfs

We report the results of a $J$-band survey for photometric variability in a sample of young, low-gravity objects using the New Technology Telescope (NTT) and the United Kingdom InfraRed Telescope (UKIRT). Surface gravity is a key parameter in the atmospheric properties of brown dwarfs and this is the first large survey that aims to test the gravity dependence of variability properties. We do a full analysis of the spectral signatures of youth and assess the group membership probability of each target using membership tools from the literature. This results in a 30 object sample of young low-gravity brown dwarfs. Since we are lacking in objects with spectral types later than L9, we focus our statistical analysis on the L0-L8.5 objects. We find that the variability occurrence rate of L0-L8.5 low-gravity brown dwarfs in this survey is $30^{+16}_{-8}\%$. We reanalyse the results of Radigan 2014 and find that the field dwarfs with spectral types L0-L8.5 have a variability occurrence rate of $11^{+13}_{-4}\%$. We determine a probability of $98\%$ that the samples are drawn from different distributions. This is the first quantitative indication that the low-gravity objects are more likely to be variable than the field dwarf population. Furthermore, we present follow-up $J_S$ and $K_S$ observations of the young, planetary-mass variable object PSO 318.5-22 over three consecutive nights. We find no evidence of phase shifts between the $J_S$ and $K_S$ bands and find higher $J_S$ amplitudes. We use the $J_S$ lightcurves to measure a rotational period of $8.45\pm0.05~$hr for PSO 318.5-22.Comment: accepted for publication in MNRA

BDSIM: An Accelerator Tracking Code with Particle-Matter Interactions

Beam Delivery Simulation (BDSIM) is a program that simulates the passage of particles in a particle accelerator. It uses a suite of standard high energy physics codes (Geant4, ROOT and CLHEP) to create a computational model of a particle accelerator that combines accurate accelerator tracking routines with all of the physics processes of particles in Geant4. This unique combination permits radiation and detector background simulations in accelerators where both accurate tracking of all particles is required over long range or over many revolutions of a circular machine, as well as interaction with the material of the accelerator.Comment: 20 pages, 17 figures. Accepted for publication 28th Jan 202

Room-Temperature Optical Picocavities below 1 nm3 Accessing Single-Atom Geometries.

Reproducible confinement of light on the nanoscale is essential for the ability to observe and control chemical reactions at the single-molecule level. Here we reliably form millions of identical nanocavities and show that the light can be further focused down to the subnanometer scale via the creation of picocavities, single-adatom protrusions with angstrom-level resolution. For the first time, we stabilize and analyze these cavities at room temperatures through high-speed surface-enhanced Raman spectroscopy on specifically selected molecular components, collecting and analyzing more than 2 million spectra. Data obtained on these picocavities allows us to deduce structural information on the nanoscale, showing that thiol binding to gold destabilizes the metal surface to optical irradiation. Nitrile moieties are found to stabilize picocavities by 10-fold against their disappearance, typically surviving for >1 s. Such constructs demonstrate the accessibility of single-molecule chemistry under ambient conditions