Isolating quantum coherence with pathway-selective coherent multi-dimensional spectroscopy

Coherent coupling between spatially separated systems has long been explored as a necessary requirement for quantum information and cryptography. Recent discoveries suggest such phenomena appear in a much wider range of processes, including light-harvesting in photosynthesis. These discoveries have been facilitated by developments in coherent multi-dimensional spectroscopy (CMDS) that allow interactions between different electronic states to be identified in crowded spectra. For complex systems, however, spectral broadening and multiple overlapping peaks limit the ability to separate, identify and properly analyse all contributions. Here we demonstrate how pathway-selective CMDS can overcome these limitations to reveal, isolate and allow detailed analysis of weak coherent coupling between spatially separated excitons localised to different semiconductor quantum wells. Selective excitation of the coherence pathways, by spectrally shaping the laser pulses, provides access to previously hidden details and enables quantitative analysis that can facilitate precise and detailed understanding of interactions in this and other complex systems

Time resolved structural dynamics of butadiyne-linked porphyrin dimers

In this work the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump / broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through addition of a ligand, provide conclusive evidence for the twisting motion performed by the porphyrin dimer in solution

A Consistent Dark Matter Interpretation For CoGeNT and DAMA/LIBRA

In this paper, we study the recent excess of low energy events observed by the CoGeNT collaboration and the annual modulation reported by the DAMA/LIBRA collaboration, and discuss whether these signals could both be the result of the same elastically scattering dark matter particle. We find that, without channeling but when taking into account uncertainties in the relevant quenching factors, a dark matter candidate with a mass of approximately ~7.0 GeV and a cross section with nucleons of sigma_{DM-N} ~2x10^-4 pb (2x10^-40 cm^2) could account for both of these observations. We also comment on the events recently observed in the oxygen band of the CRESST experiment and point out that these could potentially be explained by such a particle. Lastly, we compare the region of parameter space favored by DAMA/LIBRA and CoGeNT to the constraints from XENON 10, XENON 100, and CDMS (Si) and find that these experiments cannot at this time rule out a dark matter interpretation of these signals.Comment: 8 pages, 6 figure

Mapping the Excited‐State Potential Energy Surface of a Photomolecular Motor

A detailed understanding of the operation and efficiency of unidirectional photomolecular rotary motors is essential for their effective exploitation in molecular nanomachines. Unidirectional motion relies on light‐driven conversion from a stable (1 a) to a metastable (1 b) conformation, which then relaxes through a thermally driven helix inversion in the ground state. The excited‐state surface has thus far only been experimentally characterised for 1 a. Here we probe the metastable, 1 b, excited state, utilising ultrafast transient absorption and femtosecond stimulated Raman spectroscopy. These reveal that the “dark” excited‐state intermediate between 1 a and 1 b has a different lifetime and structure depending on the initial ground‐state conformation excited. This suggests that the reaction coordinate connecting 1 a to 1 b differs to that for the reverse photochemical process. The result is contrasted with earlier calculations

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

Control of polymorphism in coronene by the application of magnetic fields

Coronene, a polyaromatic hydrocarbon, has been crystallized for the first time in a different polymorph using a crystal growth method that utilizes magnetic fields to access a unit cell configuration that was hitherto unknown. Crystals grown in magnetic field of 1 T are larger, have a different appearance to those grown in zero field and retain their structure in ambient conditions. We identify the new form, beta-coronene, as the most stable at low temperatures. As a result of the new supramolecular configuration we report significantly altered electronic, optical and mechanical properties.Comment: 32 pages, 17 figure

An introduction to communicating science

It is becoming increasingly recognised that students in Higher Education must acquire the skills necessary for professional and personal development, as well as for academic progress. The media have recently focused on the issue of declining public interest in the sciences and the lack of accurate reporting of science. We have developed a new programme, which endeavours to address both issues involving a three day intensive course covering writing, TV and radio. In addition to the targeted activities of learning the skills of science communication, the programme encourages partnerships, and exploits the resources and expertise available from various institutions. The undertaking of this type of programme is not limited to the acquisition of time slots in a studio such as Bush House. Most university campuses are now home to their own recording studios and even have television facilities. However, the programme requires only a video camera and audio recording equipment. The success of this science communication module and oftwo others run by MOAC and CBC (Team Development and Decision-making and Leadership) has encouraged us to develop a complete postgraduate certificate in transferable skills. We anticipate the certificate will be a valuable vehicle for consolidating and enhancing the training discussed in this article