Perceived Noise Analysis for Offset Jets Applied to Commercial Supersonic Aircraft

A systems analysis was performed with experimental jet noise data, engineaircraft performance codes and aircraft noise prediction codes to assess takeoff noise levels and mission range for conceptual supersonic commercial aircraft. A parametric study was done to identify viable engine cycles that meet NASAs N+2 goals for noise and performance. Model scale data from offset jets was used as input to the aircraft noise prediction code to determine the expected sound levels for the lateral certification point where jet noise dominates over all other noise sources. The noise predictions were used to determine the optimal orientation of the offset nozzles to minimize the noise at the lateral microphone location. An alternative takeoff procedure called programmed lapse rate was evaluated for noise reduction benefits. Results show there are two types of engines that provide acceptable range performance; one is a standard mixed-flow turbofan with a single-stage fan, and the other is a three-stream variable-cycle engine with a multi-stage fan. The engine with a single-stage fan has a lower specific thrust and is 8 to 10 EPNdB quieter for takeoff. Offset nozzles reduce the noise directed toward the thicker side of the outer flow stream, but have less benefit as the core nozzle pressure ratio is reduced and the bypass-to-core area ratio increases. At the systems level for a three-engine N+2 aircraft with full throttle takeoff, there is a 1.4 EPNdB margin to Chapter 3 noise regulations predicted for the lateral certification point (assuming jet noise dominates). With a 10 reduction in thrust just after takeoff rotation, the margin increases to 5.5 EPNdB. Margins to Chapter 4 and Chapter 14 levels will depend on the cumulative split between the three certification points, but it appears that low specific thrust engines with a 10 reduction in thrust (programmed lapse rate) can come close to meeting Chapter 14 noise levels. Further noise reduction is possible with additional reduction in takeoff thrust using programmed lapse rate, but studies are needed to investigate the practical limits for safety and takeoff regulations

Characterizing Mode Anharmonicity and Huang–Rhys Factors Using Models of Femtosecond Coherence Spectra

Femtosecond laser pulses readily produce coherent quantum beats in transient–absorption spectra. These oscillatory signals often arise from molecular vibrations and therefore may contain information about the excited-state potential energy surface near the Franck–Condon region. Here, by fitting the measured spectra of two laser dyes to microscopic models of femtosecond coherence spectra (FCS) arising from molecular vibrations, we classify coherent quantum-beat signals as fundamentals or overtones and quantify their Huang–Rhys factors and anharmonicity values. We discuss the extracted Huang–Rhys factors in the context of quantum-chemical computations. This work solidifies the use of FCS for analysis of coherent quantum beats arising from molecular vibrations, which will aid studies of molecular aggregates and photosynthetic proteins

Galaxy Clusters in the IRAC Dark Field. II. Mid-Infrared Sources

We present infrared (IR) luminosities, star formation rates (SFR), colors, morphologies, locations, and active galactic nuclei (AGNs) properties of 24 μm detected sources in photometrically detected high-redshift clusters in order to understand the impact of environment on star formation (SF) and AGN evolution in cluster galaxies. We use three newly identified z = 1 clusters selected from the IRAC dark field; the deepest ever mid-IR survey with accompanying, 14 band multiwavelength data including deep Hubble Space Telescope imaging and deep wide-area Spitzer MIPS 24 μm imaging. We find 90 cluster members with MIPS detections within two virial radii of the cluster centers, of which 17 appear to have spectral energy distributions dominated by AGNs and the rest dominated by SF. We find that 43% of the star-forming sample have IR luminosities L_(IR) > 10^(11) L_☉(luminous IR galaxies). The majority of sources (81%) are spirals or irregulars. A large fraction (at least 25%) show obvious signs of interactions. The MIPS-detected member galaxies have varied spatial distributions as compared to the MIPS-undetected members with one of the three clusters showing SF galaxies being preferentially located on the cluster outskirts, while the other two clusters show no such trend. Both the AGN fraction and the summed SFR of cluster galaxies increase from redshift zero to one, at a rate that is a few times faster in clusters than over the same redshift range in the field. Cluster environment does have an effect on the evolution of both AGN fraction and SFR from redshift one to the present, but does not affect the IR luminosities or morphologies of the MIPS sample. SF happens in the same way regardless of environment making MIPS sources look the same in the cluster and field, however the cluster environment does encourage a more rapid evolution with time as compared to the field

Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates

Molecular aggregates are of interest to a broad range of fields including light harvesting, organic optoelectronics, and nanoscale computing. In molecular aggregates, nonradiative decay pathways may emerge that were not present in the constituent molecules. Such nonradiative decay pathways may include singlet fission, excimer relaxation, and symmetry-breaking charge transfer. Singlet fission, sometimes referred to as excitation multiplication, is of great interest to the fields of energy conversion and quantum information. For example, endothermic singlet fission, which avoids energy loss, has been observed in covalently bound, linear perylene trimers and tetramers. In this work, the electronic structure and excited-state dynamics of dimers of a perylene derivative templated using DNA were investigated. Specifically, DNA Holliday junctions were used to template the aggregation of two perylene molecules covalently linked to a modified uracil nucleobase through an ethynyl group. The perylenes were templated in the form of monomer, transverse dimer, and adjacent dimer configurations. The electronic structure of the perylene monomers and dimers were characterized via steady-state absorption and fluorescence spectroscopy. Initial insights into their excited-state dynamics were gleaned from relative fluorescence intensity measurements, which indicated that a new nonradiative decay pathway emerges in the dimers. Femtosecond visible transient absorption spectroscopy was subsequently used to elucidate the excited-state dynamics. A new excited-state absorption feature grows in on the tens of picosecond timescale in the dimers, which is attributed to the formation of perylene anions and cations resulting from symmetry-breaking charge transfer. Given the close proximity required for symmetry-breaking charge transfer, the results shed promising light on the prospect of singlet fission in DNA-templated molecular aggregates

Probing DNA Structural Heterogeneity by Identifying Conformational Subensembles of a Bicovalently Bound Cyanine Dye

DNA is a re-configurable, biological information-storage unit, and much remains to be learned about its heterogeneous structural dynamics. For example, while it is known that molecular dyes templated onto DNA exhibit increased photostability, the mechanism by which the structural dynamics of DNA affect the dye photophysics remains unknown. Here, we use femtosecond, two-dimensional electronic spectroscopy measurements of a cyanine dye, Cy5, to probe local conformations in samples of single-stranded DNA (ssDNA–Cy5), double-stranded DNA (dsDNA–Cy5), and Holliday junction DNA (HJ–DNA–Cy5). A line shape analysis of the 2D spectra reveals a strong excitation–emission correlation present in only the dsDNA–Cy5 complex, which is a signature of inhomogeneous broadening. Molecular dynamics simulations support the conclusion that this inhomogeneous broadening arises from a nearly degenerate conformer found only in the dsDNA–Cy5 complex. These insights will support future studies on DNA’s structural heterogeneity

Tuning Between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates

Molecular excitons, which propagate spatially via electronic energy transfer, are central to numerous applications including light harvesting, organic optoelectronics, and nanoscale computing; they may also benefit applications such as photothermal therapy and photoacoustic imaging through the local generation of heat via rapid excited-state quenching. Here we show how to tune between energy transfer and quenching for heterodimers of the same pair of cyanine dyes by altering their spatial configuration on a DNA template. We assemble “transverse” and “adjacent” heterodimers of Cy5 and Cy5.5 using DNA Holliday junctions. We find that the transverse heterodimers exhibit optical properties consistent with excitonically interacting dyes and fluorescence quenching, while the adjacent heterodimers exhibit optical properties consistent with nonexcitonically interacting dyes and disproportionately large Cy5.5 emission, suggestive of energy transfer between dyes. We use transient absorption spectroscopy to show that quenching in the transverse heterodimer occurs via rapid nonradiative decay to the ground state (∼31 ps) and that in the adjacent heterodimer rapid energy transfer from Cy5 to Cy5.5 (∼420 fs) is followed by Cy5.5 excited-state relaxation (∼700 ps). Accessing such drastically different photophysics, which may be tuned on demand for different target applications, highlights the utility of DNA as a template for dye aggregation

Excited-State Lifetimes of DNA-Templated Cyanine Dimer, Trimer, and Tetramer Aggregates: The Role of Exciton Delocalization, Dye Separation, and DNA Heterogeneity

DNA-templated molecular (dye) aggregates are a novel class of materials that have garnered attention in a broad range of areas including light harvesting, sensing, and computing. Using DNA to template dye aggregation is attractive due to the relative ease with which DNA nanostructures can be assembled in solution, the diverse array of nanostructures that can be assembled, and the ability to precisely position dyes to within a few Angstroms of one another. These factors, combined with the programmability of DNA, raise the prospect of designer materials custom tailored for specific applications. Although considerable progress has been made in characterizing the optical properties and associated electronic structures of these materials, less is known about their excited-state dynamics. For example, little is known about how the excited-state lifetime, a parameter essential to many applications, is influenced by structural factors, such as the number of dyes within the aggregate and their spatial arrangement. In this work, we use a combination of transient absorption spectroscopy and global target analysis to measure excited-state lifetimes in a series of DNA-templated cyanine dye aggregates. Specifically, we investigate six distinct dimer, trimer, and tetramer aggregates—based on the ubiquitous cyanine dye Cy5—templated using both duplex and Holliday junction DNA nanostructures. We find that these DNA-templated Cy5 aggregates all exhibit significantly reduced excited-state lifetimes, some by more than 2 orders of magnitude, and observe considerable variation among the lifetimes. We attribute the reduced excited-state lifetimes to enhanced nonradiative decay and proceed to discuss various structural factors, including exciton delocalization, dye separation, and DNA heterogeneity, that may contribute to the observed reduction and variability of excited-state lifetimes. Guided by insights from structural modeling, we find that the reduced lifetimes and enhanced nonradiative decay are most strongly correlated with the distance between the dyes. These results inform potential tradeoffs between dye separation, excitonic coupling strength, and excited-state lifetime that motivate deeper mechanistic understanding, potentially via further dye and dye template design

Rotaxane Rings Promote Oblique Packing and Extended Lifetimes in DNA-Templated Molecular Dye Aggregates

Molecular excitons play a central role in natural and artificial light harvesting, organic electronics, and nanoscale computing. The structure and dynamics of molecular excitons, critical to each application, are sensitively governed by molecular packing. Deoxyribonucleic acid (DNA) templating is a powerful approach that enables controlled aggregation via sub-nanometer positioning of molecular dyes. However, finer sub-Angstrom control of dye packing is needed to tailor excitonic properties for specific applications. Here, we show that adding rotaxane rings to squaraine dyes templated with DNA promotes an elusive oblique packing arrangement with highly desirable optical properties. Specifically, dimers of these squaraine:rotaxanes exhibit an absorption spectrum with near-equal intensity excitonically split absorption bands. Theoretical analysis indicates that the transitions are mostly electronic in nature and only have similar intensities over a narrow range of packing angles. Compared with squaraine dimers, squaraine:rotaxane dimers also exhibit extended excited-state lifetimes and less structural heterogeneity. The approach proposed here may be generally useful for optimizing excitonic materials for a variety of applications ranging from solar energy conversion to quantum information science

Oblique Packing and Tunable Excitonic Coupling in DNA-Templated Squaraine Rotaxane Dimer Aggregates

When molecules are aggregated such that their excited states form delocalized excitons, their spatial arrangement, or packing, can be coarsely controlled by templating and finely controlled by chemical substitution; however, challenges remain in controlling their packing on intermediate length scales. Here, we use an approach based on mechanically interlocked molecules to promote an elusive oblique packing arrangement in a series of three squaraine rotaxane dimers. We template the squaraine rotaxane dimers using DNA and observe two excitonically split bands of near-equal intensity in their absorption spectra – a distinct signature of oblique packing, validated by theoretical modeling of the experimental results. Additional fine control of packing is demonstrated by fluorinating the macrocycle of the rotaxane, which promotes denser packing and stronger excitonic interactions