Polariton condensation and surface enhanced Raman in spherical ZnO microcrystals

Preparation and characterization of polariton Bose–Einstein condensates in micro-cavities of high quality are at the frontier of contemporary solid state physics. Here, we report on three-dimensional polariton condensation and confinement in pseudo-spherical ZnO microcrystals. The boundary of micro-spherical ZnO resembles a stable cavity that enables sufficient coupling of radiation with material response. Exciting under tight focusing at the low frequency side of the bandgap, we detect efficiency and spectral nonlinear dependencies, as well as signatures of spatial delocalization of the excited states which are characteristics of dynamics in polariton droplets. Expansion of the photon component of the condensate boosts the leaky field beyond the boundary of the ZnO microcrystals. Using this, we observe surface polariton field enhanced Raman responses at the interface of ZnO microspheres. The results demonstrate how readily available spherical semiconductor microstructures facilitate engineering of polariton based electronic states and sensing elements for diagnostics at interfaces

Computational Complexity of Synchronization under Regular Commutative Constraints

Here we study the computational complexity of the constrained synchronization problem for the class of regular commutative constraint languages. Utilizing a vector representation of regular commutative constraint languages, we give a full classification of the computational complexity of the constraint synchronization problem. Depending on the constraint language, our problem becomes PSPACE-complete, NP-complete or polynomial time solvable. In addition, we derive a polynomial time decision procedure for the complexity of the constraint synchronization problem, given some constraint automaton accepting a commutative language as input.Comment: Published in COCOON 2020 (The 26th International Computing and Combinatorics Conference); 2nd version is update of the published version and 1st version; both contain a minor error, the assumption of maximality in the NP-c and PSPACE-c results (propositions 5 & 6) is missing, and of incomparability of the vectors in main theorem; fixed in this version. See (new) discussion after main theore

From phage display to structure: interplay of enthalpy and entropy in binding of LDHSLHS polypeptide to silica

Polypeptide based biosilica composites show promise as next generation multi-functional nano-platforms for diagnostics and bio-catalytic applications. Following identification of a strong silica binder (LDHSLHS) by phage display, we conduct structural analysis of the polypeptide at the interface with amorphous silica nanoparticles in an aqueous environment. Our approach relies on modelling of Infrared and Raman spectral responses using predictions of molecular dynamics simulations and quantum studies of the normal modes for several potential structures. By simultaneously fitting both Infrared and Raman responses in the Amide spectral region, we show that the main structural conformer has a beta-like central region and helix-twisted terminals. Classical simulations, as conducted previously (Chem. Mater., 2014, 26, 5725), predict that association of the main structure with the interface is stimulated by electrostatic interactions though surface binding also requires spatially distributed sodium ions to compensate negatively charged acidic silanol groups. Accordingly, diffusion of sodium ions would contribute to a stochastic character of the peptides association with the surface. Consistent with the described dynamics at the interface, results from isothermal titration calorimetry (ITC) confirm significant enhancement of polypeptide binding to silica under higher concentrations of Na+. The results of this study suggest that the tertiary structure of a phage capsid protein plays a significant role in regulating the conformation of peptide LDHSLHS, increasing its binding to silica during the phage display process. The results presented here support design-led engineering of polypeptide-silica nanocomposites for bio-technological applications

Probing microwave fields and enabling in-situ experiments in a transmission electron microscope.

A technique is presented whereby the performance of a microwave device is evaluated by mapping local field distributions using Lorentz transmission electron microscopy (L-TEM). We demonstrate the method by measuring the polarisation state of the electromagnetic fields produced by a microstrip waveguide as a function of its gigahertz operating frequency. The forward and backward propagating electromagnetic fields produced by the waveguide, in a specimen-free experiment, exert Lorentz forces on the propagating electron beam. Importantly, in addition to the mapping of dynamic fields, this novel method allows detection of effects of microwave fields on specimens, such as observing ferromagnetic materials at resonance

Structural and electronic properties of 3,3-azothiophene photo-switching systems

Diversity of photo-switching structural elements open up new opportunities in the engineering of light driven reshaping of matter, in catalysis on-click including photodynamic cancer therapy, in light sensitive transport control and in data storage. Assisted with quantum calculations we explore the photo-physical properties of novel 3,3-azothiophene molecular systems, the synthesis of which we reported recently. In the considered azothiophenes, upon exposure to radiation at 365 nm and at 530 nm, we observed effective anti(trans) to syn(cis) and syn(cis) to anti(trans) isomerization of the -N=N- moiety, respectively. In contrast to azobenzene based photo-switchable molecular systems, the syn(cis) to anti(trans) isomerization in the azothiophenes studied, does not take place at 22 oC in the dark. Temperature dependent experiments and theoretical studies suggest a slightly higher barrier for such processes than for azobenzene which we attribute to specific structural and electronic properties of the thiophene ring and the nature of the side groups. We discuss the potential of the observed properties in the development of novel molecular photo-switching machinery to promote biocatalytic applications at interfaces

Do material discontinuities in silica affect vibration modes?

Structural properties of bioinorganic composites are of current interest in the areas of drug delivery, bone repair and biomimetics. In such composite systems, structural analysis is enhanced when we combine methods of spectroscopy and simulation. Depending on size and shape, structural discontinuities of inorganic matter may modulate the optical response of a bound molecule. Using Density Functional Theory we explore the effects of a local field next to the surface of a silica cluster on frequencies of methyl stretching modes of associated methanols. Computation results predict that the electrostatic potential modulated by structural discontinuities of silica should not contribute to any systematic frequency shifts for normal modes of a guest molecule. Regardless of position, the methyl stretching modes of methanol demonstrate sensitivity only to the local chemistry of bonding with silanols, which may lead either to a low or to high frequency shift for vibrations. In support, experimental studies of deuterated methanol at impurity levels in water show uniform broadening of resonances of Carbon–Deuterium stretching modes in the presence of both crystalline and amorphous silica nanoparticles. The significance of these findings is that the spectral responses of guest molecules on such surfaces should not be subject to bias introduced by edge effects

Anchoring of a hydrophobic heptapeptide (AFILPTG) on silica facilitates peptide unfolding at the abiotic-biotic interface

A hydrophobic heptapeptide, sequence AFILPTG, as part of a phage capsid protein binds effectively to silica particles carrying negative charge. Here, we explore the silica binding activity of the sequence as a short polypeptide with polar N and C terminals. To describe the structural changes that occur on binding, we fit experimental infrared, Raman and circular dichroism data for a number of structures simulated in the full configuration space of the hepta-peptide using replica exchange molecular dynamics. Quantum chemistry was used to compute normal modes of infrared and Raman spectra and establish a relationship to structures from MD data. To interpret the circular dichroism data, instead of empirical factoring of optical activity into helical/sheet/random components, we exploit natural transition orbital theory and specify the contributions of backbone amide units, side chain functional groups, water, sodium ions and silica to the observed transitions. Computed optical responses suggest a less folded backbone and importance of the N-terminal when close to silica. We further discuss the thermodynamics of the interplay of charged and hydrophobic moieties of the polypeptide on association with the silica surface. The outcomes of this study may assist in the engineering of novel artificial bio-silica heterostructures

Indigo chromophores and pigments: structure and dynamics

In this study, we explore the molecular mechanisms of the stability of indigo chromophores and pigments. Assisted with density functional theory, we compare visible, infrared and Raman spectral properties of model molecules, chromophores and pigments derived from living organisms. Using indigo carmine as a representative model system, we characterize the structure and dynamics of the chromophore in the first electronic excited state using femtosecond visible pump-infrared probe spectroscopy. Results of experiments and theoretical studies indicate that, while the trans geometry is strongly dominant in the electronic ground state, upon photoexcitation, in the Franck-Condon region, some molecules may experience isomerization and proton transfer dynamics. If this happens, however, the normal modes of the trans geometry of the electronic excited state are reconfirmed within several hundred femtoseconds. Supported by quantum theory, first, we ascribe stabilization of the trans geometry in the Franck-Condon region to the reactive character of the potential energy surface for the indigo chromophore when under the cis geometry in the electronic excited state. Second, we suggest that a conical intersection crossing, due to the high barrier along the isomerization pathway in the ground state, would provide for the effective relaxation and observed dominance of the trans geometry of the chromophore in the ground state. Planarity of the chromophore under the trans geometry assists effective dissipation of energy via a cascade of in-plane C-C, C-O···H-N stretchings and C-C-C bending modes delocalized over the molecular mainframe. The described mechanisms help to explain the remarkable photo-stability of indigo chromophores

On the Number of Synchronizing Colorings of Digraphs

We deal with $k$-out-regular directed multigraphs with loops (called simply \emph{digraphs}). The edges of such a digraph can be colored by elements of some fixed $k$-element set in such a way that outgoing edges of every vertex have different colors. Such a coloring corresponds naturally to an automaton. The road coloring theorem states that every primitive digraph has a synchronizing coloring. In the present paper we study how many synchronizing colorings can exist for a digraph with $n$ vertices. We performed an extensive experimental investigation of digraphs with small number of vertices. This was done by using our dedicated algorithm exhaustively enumerating all small digraphs. We also present a series of digraphs whose fraction of synchronizing colorings is equal to $1-1/k^d$, for every $d \ge 1$ and the number of vertices large enough. On the basis of our results we state several conjectures and open problems. In particular, we conjecture that $1-1/k$ is the smallest possible fraction of synchronizing colorings, except for a single exceptional example on 6 vertices for $k=2$.Comment: CIAA 2015. The final publication is available at http://link.springer.com/chapter/10.1007/978-3-319-22360-5_1

Topological Crystalline Insulators in the SnTe Material Class

Topological crystalline insulators are new states of matter in which the topological nature of electronic structures arises from crystal symmetries. Here we predict the first material realization of topological crystalline insulator in the semiconductor SnTe, by identifying its nonzero topological index. We predict that as a manifestation of this nontrivial topology, SnTe has metallic surface states with an even number of Dirac cones on high-symmetry crystal surfaces such as {001}, {110} and {111}. These surface states form a new type of high-mobility chiral electron gas, which is robust against disorder and topologically protected by reflection symmetry of the crystal with respect to {110} mirror plane. Breaking this mirror symmetry via elastic strain engineering or applying an in-plane magnetic field can open up a continuously tunable band gap on the surface, which may lead to wide-ranging applications in thermoelectrics, infrared detection, and tunable electronics. Closely related semiconductors PbTe and PbSe also become topological crystalline insulators after band inversion by pressure, strain and alloying.Comment: submitted on Feb. 10, 2012; to appear in Nature Communications; 5 pages, 4 figure