Ultrafast Structure and Dynamics in the Thermally Activated Delayed Fluorescence of a Carbene-Metal-Amide

Thermally activated delayed fluorescence has enormous potential for the development of efficient light emitting diodes. A recently discovered class of molecules (the carbene – metal – amides, CMAs) are exceptionally promising as they combine the small singlet - triplet energy gap required for thermal activation with a large transition moment for emission. Calculations suggest that excited state structural dynamics modulate the critical coupling between singlet and triplet states, but do not agree on the nature of those dynamics. Here we report ultrafast time resolved transient absorption and Raman studies of CMA photodynamics. The measurements reveal complex structural evolution following intersystem crossing on the tens to hundreds of picoseconds timescale, and a change in the low frequency vibrational spectrum between singlet and triplet states. The latter is assigned to a change in frequency or amplitude associated with a Raman active mode localized on the metal centre

Plausible home stars of the interstellar object 'Oumuamua found in Gaia DR2

The first detected interstellar object 'Oumuamua that passed within 0.25au of the Sun on 2017 September 9 was presumably ejected from a stellar system. We use its newly determined non-Keplerian trajectory together with the reconstructed Galactic orbits of 7 million stars from Gaia DR2 to identify past close encounters. Such an "encounter" could reveal the home system from which 'Oumuamua was ejected. The closest encounter, at 0.60pc (0.53-0.67pc, 90% confidence interval), was with the M2.5 dwarf HIP 3757 at a relative velocity of 24.7km/s, 1Myr ago. A more distant encounter (1.6pc) but with a lower encounter (ejection) velocity of 10.7km/s was with the G5 dwarf HD 292249, 3.8Myr ago. Two more stars have encounter distances and velocities intermediate to these. The encounter parameters are similar across six different non-gravitational trajectories for 'Oumuamua. Ejection of 'Oumuamua by scattering from a giant planet in one of the systems is plausible, but requires a rather unlikely configuration to achieve the high velocities found. A binary star system is more likely to produce the observed velocities. None of the four home candidates have published exoplanets or are known to be binaries. Given that the 7 million stars in Gaia DR2 with 6D phase space information is just a small fraction of all stars for which we can eventually reconstruct orbits, it is a priori unlikely that our current search would find 'Oumuamua's home star system. As 'Oumuamua is expected to pass within 1pc of about 20 stars and brown dwarfs every Myr, the plausibility of a home system depends also on an appropriate (low) encounter velocity.Comment: Accepted to The Astronomical Journa

Thermal evolution and activity of Comet 9P/Tempel 1 and simulation of a deep impact

We use a quasi 3-D thermal evolution model for a spherical comet nucleus, which takes into account the diurnal and latitudinal variation of the solar flux, but neglects lateral heat conduction. We model the thermal evolution and activity of Comet 9P/Tempel 1, in anticipation of the Deep Impact mission encounter with the comet. We also investigate the possible outcome of a projectile impact, assuming that all the energy is absorbed as thermal energy. An interesting result of this investigation, is that the estimated amount of dust ejected due to the impact is equivalent to 2--2.6 days of activity, during "quiet" conditions, at perihelion. We show that production rates of volatiles that are released in the interior of the nucleus depend strongly on the porous structure, in particular on the surface to volume ratio of the pores. We develop a more accurate model for calculating this parameter, based on a distribution of pore sizes, rather than a single, average pore size.Comment: 25 pages, 8 figures, accepted for publication in PASP (in press). For fig.xx (composite image, sec.4) and a better resolution of fig.6 see, http://geophysics.tau.ac.il/personal/gal%5Fsarid

Temporal and Spatial Aspects of Gas Release During the 2010 Apparition of Comet 103P/Hartley-2

We report measurements of eight primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, C2H2, H2CO, and NH3) and two product species (OH and NH2) in comet 103P/Hartley-2 using high dispersion infrared spectroscopy. We quantified the long- and short-term behavior of volatile release over a three-month interval that encompassed the comet's close approach to Earth, its perihelion passage, and flyby of the comet by the Deep Impact spacecraft during the EPOXI mission. We present production rates for individual species, their mixing ratios relative to water, and their spatial distributions in the coma on multiple dates. The production rates for water, ethane, HCN, and methanol vary in a manner consistent with independent measures of nucleus rotation, but mixing ratios for HCN, C2H6, & CH3OH are independent of rotational phase. Our results demonstrate that the ensemble average composition of gas released from the nucleus is well defined, and relatively constant over the three-month interval (September 18 through December 17). If individual vents vary in composition, enough diverse vents must be active simultaneously to approximate (in sum) the bulk composition of the nucleus. The released primary volatiles exhibit diverse spatial properties which favor the presence of separate polar and apolar ice phases in the nucleus, establish dust and gas release from icy clumps (and also, directly from the nucleus), and provide insights into the driver for the cyanogen (CN) polar jet. The spatial distributions of C2H6 & HCN along the near-polar jet (UT 19.5 October) and nearly orthogonal to it (UT 22.5 October) are discussed relative to the origin of CN. The ortho-para ratio (OPR) of water was 2.85 \pm 0.20; the lower bound (2.65) defines Tspin > 32 K. These values are consistent with results returned from ISO in 1997.Comment: 18 pages, 3 figures, to be published in: Astrophysical Journal Letter

Sub-wavelength surface IR imaging of soft-condensed matter

Outlined here is a technique for sub-wavelength infrared surface imaging performed using a phase matched optical parametric oscillator laser and an atomic force microscope as the detection mechanism. The technique uses a novel surface excitation illumination approach to perform simultaneously chemical mapping and AFM topography imaging with an image resolution of 200 nm. This method was demonstrated by imaging polystyrene micro-structures

Excited state dynamics in unidirectional photochemical molecular motors

Unidirectional photochemically driven molecular motors (PMMs) convert the energy of absorbed light into continuous rotational motion. As such they are key components in the design of molecular machines. The prototypical and most widely employed class of PMMs is the overcrowded alkenes, where rotational motion is driven by successive photoisomerization and thermal helix inversion steps. The efficiency of such PMMs depends upon the speed of rotation, determined by the rate of ground state thermal helix inversion, and the quantum yield of photoisomerization, which is dependent on the excited state energy landscape. The former has been optimized by synthetic modification across three generations of overcrowded alkene PMMs. These improvements have often been at the expense of photoisomerization yield, where there remains room for improvement. In this perspective we review the application of ultrafast spectroscopy to characterize the excited state dynamics in PMMs. These measurements lead to a general mechanism for all generations of PMMs, involving subpicosecond decay of a Franck–Condon excited state to populate a dark excited state which decays within picoseconds via conical intersections with the electronic ground state. The model is discussed in the context of excited state dynamics calculations. Studies of PMM photochemical dynamics as a function of solvent suggest exploitation of intramolecular charge transfer and solvent polarity as a route to controlling photoisomerization yield. A test of these ideas for a first generation motor reveals a high degree of solvent control over isomerization yield. These results suggest a pathway to fine control over the performance of future PMMs