Emission Quenching in Tetraphenylfuran Crystal: Why This Propeller-Shaped Molecule Does Not Emit in the Condensed Phase

Due to their substantial fluorescence quantum yields in the crystalline phase, propeller-shaped molecules have recently gained significant attention as potential emissive materials for optoelectronic applications. For the family of cyclopentadiene derivatives, light-emission is highly dependent on the nature of heteroatomic substitutions. In this paper, we investigate excited state relaxation pathways in the tetraphenyl-furan molecule (TPF), which in contrast with other molecules in the family, shows emission quenching in the solid-state. For the singlet manifold, our calculations show nonradiative pathways associated with C-O elongation are blocked in both vacuum and the solid state. A fraction of the population can be transferred to the triplet manifold and, subsequently, to the ground state in both phases. This process is expected to be relatively slow due to the small spin-orbit couplings between the relevant singlet-triplet states. Emission quenching in crystalline TPF seems to be in line with more efficient exciton hopping rates. Our simulations help clarify the role of conical intersections, population of the triplet states and crystalline structure in the emissive response of propeller-shaped molecules

Scalable, Time-Responsive, Digital, Energy-Efficient Molecular Circuits using DNA Strand Displacement

We propose a novel theoretical biomolecular design to implement any Boolean circuit using the mechanism of DNA strand displacement. The design is scalable: all species of DNA strands can in principle be mixed and prepared in a single test tube, rather than requiring separate purification of each species, which is a barrier to large-scale synthesis. The design is time-responsive: the concentration of output species changes in response to the concentration of input species, so that time-varying inputs may be continuously processed. The design is digital: Boolean values of wires in the circuit are represented as high or low concentrations of certain species, and we show how to construct a single-input, single-output signal restoration gate that amplifies the difference between high and low, which can be distributed to each wire in the circuit to overcome signal degradation. This means we can achieve a digital abstraction of the analog values of concentrations. Finally, the design is energy-efficient: if input species are specified ideally (meaning absolutely 0 concentration of unwanted species), then output species converge to their ideal concentrations at steady-state, and the system at steady-state is in (dynamic) equilibrium, meaning that no energy is consumed by irreversible reactions until the input again changes. Drawbacks of our design include the following. If input is provided non-ideally (small positive concentration of unwanted species), then energy must be continually expended to maintain correct output concentrations even at steady-state. In addition, our fuel species - those species that are permanently consumed in irreversible reactions - are not "generic"; each gate in the circuit is powered by its own specific type of fuel species. Hence different circuits must be powered by different types of fuel. Finally, we require input to be given according to the dual-rail convention, so that an input of 0 is specified not only by the absence of a certain species, but by the presence of another. That is, we do not construct a "true NOT gate" that sets its output to high concentration if and only if its input's concentration is low. It remains an open problem to design scalable, time-responsive, digital, energy-efficient molecular circuits that additionally solve one of these problems, or to prove that some subset of their resolutions are mutually incompatible.Comment: version 2: the paper itself is unchanged from version 1, but the arXiv software stripped some asterisk characters out of the abstract whose purpose was to highlight words. These characters have been replaced with underscores in version 2. The arXiv software also removed the second paragraph of the abstract, which has been (attempted to be) re-inserted. Also, although the secondary subject is "Soft Condensed Matter", this classification was chosen by the arXiv moderators after submission, not chosen by the authors. The authors consider this submission to be a theoretical computer science paper

Role of Conical Intersections on the Efficiency of Fluorescent Organic Molecular Crystals

Organic molecular crystals are attractive materials for luminescent applications because of their promised tunability. However, the link between the chemical structure and emissive behavior is poorly understood because of the numerous interconnected factors which are at play in determining radiative and nonradiative behaviors at the solid-state level. In particular, the decay through conical intersection dominates the nonadiabatic regions of the potential energy surface, and thus, their accessibility is a telling indicator of the luminosity of the material. In this study, we investigate the radiative mechanism for five organic molecular crystals which display a solid-state emission, with a focus on the role of conical intersections in their photomechanisms. The objective is to situate the importance of the accessibility of conical intersections with regards to emissive behavior, taking into account other nonradiative decay channels, namely, vibrational decay, and exciton hopping. We begin by giving a brief overview of the structural patterns of the five systems within a larger pool of 13 crystals for a richer comparison. We observe that because of the prevalence of sheet like and herringbone packing in organic molecular crystals, the conformational diversity of crystal dimers is limited. Additionally, similarly spaced dimers have exciton coupling values of a similar order within a 50 meV interval. Next, we focus on three exemplary cases, where we disentangle the role of nonradiative decay mechanisms and show how rotational minimum energy conical intersections in vacuum lead to puckered ones in the crystal, increasing their instability upon crystallization in typical packing motifs. In contrast, molecules with puckered conical intersections in vacuum tend to conserve this trait upon crystallization, and therefore, their quantum yield of fluorescence is determined predominantly by other nonradiative decay mechanisms

Adaptive OFDM Modulation for Underwater Acoustic Communications: Design Considerations and Experimental Results

Cataloged from PDF version of article.In this paper, we explore design aspects of adaptive modulation based on orthogonal frequency-division multiplexing (OFDM) for underwater acoustic (UWA) communications, and study its performance using real-time at-sea experiments. Our design criterion is to maximize the system throughput under a target average bit error rate (BER). We consider two different schemes based on the level of adaptivity: in the first scheme, only the modulation levels are adjusted while the power is allocated uniformly across the subcarriers, whereas in the second scheme, both the modulation levels and the power are adjusted adaptively. For both schemes we linearly predict the channel one travel time ahead so as to improve the performance in the presence of a long propagation delay. The system design assumes a feedback link from the receiver that is exploited in two forms: one that conveys the modulation alphabet and quantized power levels to be used for each subcarrier, and the other that conveys a quantized estimate of the sparse channel impulse response. The second approach is shown to be advantageous, as it requires significantly fewer feedback bits for the same system throughput. The effectiveness of the proposed adaptive schemes is demonstrated using computer simulations, real channel measurements recorded in shallow water off the western coast of Kauai, HI, USA, in June 2008, and real-time at-sea experiments conducted at the same location in July 2011. We note that this is the first paper that presents adaptive modulation results for UWA links with real-time at-sea experiments. © 2013 IEEE

Sesquicaesium hemisodium tetra­cyanidoplatinate(II) sesquihydrate

The title compound, Cs1.5Na0.5[Pt(CN)4]·1.5H2O, was isolated from solution as a salt. The tetra­cyanidoplatinate (TCP) anions are stacked in a linear quasi-one-dimensional arrangement along the b axis, with Pt⋯Pt inter­actions of 3.6321 (5) Å. The mixed alkali metal TCP contains three distinct alkali metal positions in the structure that do not show any mixed occupancy: Cs1 (site symmetry 2), Cs2 (general position) and Na1 (site symmetry ). The Na+ ion contains an octa­hedral coordination environment composed of two water mol­ecules and four N-terminal cyanides, which serve to bridge TCP anions. The Cs+ cations contain mono- and bicapped square-prismatic environments, where the square prisms are formed from cyanide N atoms with water mol­ecules capping the faces. The 1.5 water mol­ecules per formula unit are a result of two fully occupied sites, one on a general position and one on a twofold rotation axis. Weak hydrogen-bonding inter­actions are observed between one water mol­ecule and terminal N-atom acceptors from TCP, while the second water mol­ecule is not involved in hydrogen bonding

Thionation of N-Methyl- and N-Unsubstituted Thiazolidine Enaminones

The potential of the directional non-bonded 1,5-type S···O interactions to initiate an incipient stage of an in situ rearrangement of N-unsubstituted thiazolidine enaminones to the functionalized 1,2-dithioles has been demonstrated. Spectral characteristics, as well as an X-ray structural analysis of the selected rearranged product, indicate that a dynamic interconversion occurs in a solution between the 1,2-dithiole and 3,3aλ⁴,4-trithia-1-azapentalene bicylic form. The lack of the rearrangement in the case of the N-methyl substituted enaminone precursor is attributed to an unfavorable methyl migration in the last reaction step

Entanglement dynamics of two qubits under the influence of external kicks and Gaussian pulses

We have investigated the dynamics of entanglement between two spin-1/2 qubits that are subject to independent kick and Gaussian pulse type external magnetic fields analytically as well as numerically. Dyson time ordering effect on the dynamics is found to be important for the sequence of kicks. We show that "almost-steady" high entanglement can be created between two initially unentangled qubits by using carefully designed kick or pulse sequences