Correlated-electron description of the photophysics of thin films of π\pi-conjugated polymers

We extend Mulliken's theory of ground state charge transfer in a donor-acceptor complex to excited state charge transfer between pairs of identical $\pi$-conjugated oligomers, one of which is in the optically excited state and the other in the ground state, leading to the formation of a charge-transfer exciton. Within our theory, optical absorptions from the charge-transfer exciton should include a low energy intermolecular charge-transfer excitation, as well as distinct intramolecular excitations from both the neutral delocalized exciton component and the Coulombically bound polaron-pair component of the charge-transfer exciton. We report high order configuration-interaction calculations for pairs of oligomers of poly-paraphenylenevinylene (PPV) that go beyond our previous single configuration-interaction calculation and find all five excited state absorptions predicted using heuristic arguments based on the Mulliken concept. Our calculated excited state absorption spectrum exhibits strong qualitative agreement with the complete wavelength-dependent ultrafast photoinduced absorption in films of PPV derivatives, suggesting that a significant fraction of the photoinduced absorption here is from the charge-transfer exciton. We make detailed comparisons to experiments, and a testable experimental prediction

Acidic Pericellular Ph: Effects On Proteolysis And Gene Expression As Determined In 3d Models Of Breast Carcinoma

Among the non-cellular microenvironmental factors that contribute to malignancy of solid tumors is an acidic peritumoral pH. The first objective was to determine if an acidic extracellular pH observed in vivo (i.e., pHe 6.8) affects the activity of proteases, such as cathepsin B, that contribute to degradation of collagen IV by tumor cells when grown in biologically relevant three-dimensional cultures. At pHe 6.8 there were increases in pericellular active cysteine cathepsins and in degradation of DQ-collagen IV, which was partially blocked by a cathepsin B inhibitor. Imaging probes for active cysteine cathepsins localized to tumors in vivo. The amount of bound probe decreased in tumors in bicarbonate-treated mice, a treatment previously shown to increase peritumoral pHe and reduce local invasion of the tumors. Our results are consistent with the acid-mediated invasion hypothesis and with a role for cathepsin B in promoting degradation of a basement membrane protein substrate, i.e. type IV collagen, in an acidic peritumoral environment. The second objective was to use a microarray approach to identify significantly altered genes that may be of importance in the response to acidic pH in ductal carcinoma in situ (DCIS). We have found that STAT1-directed signaling is up-regulated in response to acidic pH extracellularly. Its role in altering glycolytic pathways suggests an important role for this transcription factor in the development of an acidic extracellular pH

Competition between Electromagnetically Induced Transparency and Raman Processes

We present a theoretical formulation of competition among electromagnetically induced transparency (EIT) and Raman processes. The latter become important when the medium can no longer be considered to be dilute. Unlike the standard formulation of EIT, we consider all fields applied and generated as interacting with both the transitions of the $\Lambda$ scheme. We solve Maxwell equations for the net generated field using a fast-Fourier-transform technique and obtain predictions for the probe, control and Raman fields. We show how the intensity of the probe field is depleted at higher atomic number densities due to the build up of multiple Raman fields.Comment: 3.5 pages, 7 figure

Globular Cluster Systems in Brightest Cluster Galaxies. III: Beyond Bimodality

We present new deep photometry of the rich globular cluster (GC) systems around the Brightest Cluster Galaxies UGC 9799 (Abell 2052) and UGC 10143 (Abell 2147), obtained with the HST ACS and WFC3 cameras. For comparison, we also present new reductions of similar HST/ACS data for the Coma supergiants NGC 4874 and 4889. All four of these galaxies have huge cluster populations (to the radial limits of our data, comprising from 12000 to 23000 clusters per galaxy). The metallicity distribution functions (MDFs) of the GCs can still be matched by a bimodal-Gaussian form where the metal-rich and metal-poor modes are separated by ~0.8 dex, but the internal dispersions of each mode are so large that the total MDF becomes very broad and nearly continuous from [Fe/H] = -2.4 to Solar. There are, however, significant differences between galaxies in the relative numbers of \emph{metal-rich} clusters, suggesting that they underwent significantly different histories of mergers with massive, gas-rich halos. Lastly, the proportion of metal-poor GCs rises especially rapidly outside projected radii R > 4 R_eff, suggesting the importance of accreted dwarf satellites in the outer halo. Comprehensive models for the formation of GCs as part of the hierarchical formation of their parent galaxies will be needed to trace the systematic change in structure of the MDF with galaxy mass, from the distinctly bimodal form in smaller galaxies up to the broad continuum that we see in the very largest systems.Comment: In press for Astrophysical Journa

Radial vibration measurements directly from rotors using laser vibrometry: The effects of surface roughness, instrument misalignments and pseudo-vibration

Laser Doppler vibrometry (LDV) offers an attractive solution when radial vibration measurement directly from a rotor surface is required. Research to date has demonstrated application on polished-circular rotors and rotors coated with retro-reflective tape. In the latter case, however, a significant cross-sensitivity to the orthogonal radial vibration component occurs and post-processing is required to resolve individual radial vibration components. Until now, the fundamentally different behaviour observed between these cases has stood as an inconsistency in the published literature, symptomatic of the need to understand the effect of surface roughness. This paper offers the first consistent mathematical description of the polished-circular and rough rotor behaviours, combined with an experimental investigation of the relationship between surface roughness and cross-sensitivity. Rotors with surface roughness up to 10 nm satisfy the polished-circular rotor definition if vibration displacement is below 100% beam diameter, for a 90 μm beam, and below 40% beam diameter, for a 520 μm beam. On rotors with roughness between 10 nm and 50 nm, the polished-circular rotor definition is satisfied for vibration displacements up to 25% beam diameter, for a 90 μm beam, and up to 10% beam diameter, for a 520 μm beam. As roughness increases, cross-sensitivity increases but only rotors coated in retro-reflective tape satisfied the rough rotor definition fully. Consequently, when polished-circular surfaces are not available, rotor surfaces must be treated with retro-reflective tape and measurements post-processed to resolve individual vibration components. Through simulations, the value of the resolution and correction algorithms that form the post-processor has been demonstrated quantitatively. Simulations incorporating representative instrument misalignments and measurement noise have enabled quantification of likely error levels in radial vibration measurements. On a polished-circular rotor, errors around 0.2% for amplitude and 2 mrad for phase are likely, rising a little at the integer orders affected by pseudo-vibration. Higher pseudo-vibration levels and the need for resolution increase errors in the rough rotor measurements, especially around the synchronous frequency where errors reach 20% by amplitude and 100 mrad for phase. Outside a range of half an order either side of first order, errors are ten times lower and beyond fifth order errors are similar to those for the polished-circular rotor. Further simulations were performed to estimate sensitivities to axial vibration, speed variation and bending vibrations. © 2012 Elsevier Ltd

The Globular Cluster Systems around NGC 3311 and NGC 3309

We present extensive new photometry in (g',i') of the large globular cluster (GC) system around NGC 3311, the central cD galaxy in the Hydra cluster. Our GMOS data cover a 5.5' field of view and reach a limiting magnitude i' = 26, about 0.5 magnitude fainter than the turnover point of the GC luminosity function. We find that NGC 3311 has a huge population of ~16, 000 GCs, closely similar to the prototypical high specific frequency Virgo giant M87. The color-magnitude distribution shows that the metal-poor blue GC sequence and the metal-richer red sequence are both present, with nearly equal numbers of clusters. Bimodal fits to the color distributions confirm that the blue sequence shows the same trend of progressively increasing metallicity with GC mass that has previously been found in many other large galaxies; the correlation we find corresponds to a scaling of GC metallicity with mass of Z ~ M^0.6 . By contrast, the red sequence shows no change of mean metallicity with mass, but it shows an upward extension to much higher than normal luminosity into the UCD-like range, strengthening the potential connections between massive GCs and UCDs. The GC luminosity function, which we measure down to the turnover point at M_I = -8.4, also has a normal form like those in other giant ellipticals. Within the Hydra field, another giant elliptical NGC 3309 is sitting just 100" from the cD NGC 3311. We use our data to solve simultaneously for the spatial structure and total GC populations of both galaxies at once. Their specific frequencies are S_N (NGC 3311) = 12.5 +/- 1.5 and S_N (NGC 3309) = 0.6 +/-0.4. NGC 3311 is completely dominant and entirely comparable with other cD-type systems such as M87 in Virgo.Comment: 15 pages, 15 figures. Accepted to the Astrophysical Journal. Version with higher resolution figures is available at http://www.thewehners.net/astro/papers/wehner_n3311_highres.pd

Photogeneration Dynamics of a Soliton Pair in Polyacetylene

Dynamical process of the formation of a soliton pair from a photogenerated electron-hole pair in polyacetylene is studied numerically by adopting the SSH Hamiltonian. A weak local disorder is introduced in order to trigger the formation. Starting from an initial configuration with an electron at the bottom of the conduction band and a hole at the top of the valence band, separated by the Peierls gap, the time dependent Schr${\rm \ddot{o}}$ndinger equation for the electron wave functions and the equation of motion for the lattice displacements are solved numerically. After several uniform oscillations of the lattice system at the early stage, a large distortion corresponding to a pair of a soliton and an anti-soliton develops from a point which is determined by the location and type of the disorder. In some cases, two solitons run in opposite directions, leaving breather like oscillations behind, and in other cases they form a bound state emitting acoustic lattice vibrational modes.Comment: 16 pages 7 figure

Mid-Infrared and Submillimeter Observations of the Illuminating Source of McNeil's Variable Nebula

We present post-outburst observations of the mid-infrared spectrum and submillimeter continuum of the illuminating source of the newly-discovered McNeil's Nebula in the L1630 region of Orion. The 12 micron flux of this source has increased by a factor of 25 after the outburst, whereas the submillimeter continuum remains at its pre-outburst level. The bolometric luminosity has increased by at least an order of magnitude, to ~34 L_sun, and is likely less than 90 L_sun. The mid-infrared spectrum exhibits a strong and red continuum with no emission or absorption features. The infrared slope of the spectral energy distribution characterizes the illuminating source as a flat-spectrum protostar, in both its active and quiescent states. New CO spectral line observations show no evidence for a molecular outflow.Comment: submitted to ApJ

Multi-physics analysis of valve train systems: from system level to microscale interactions

The paper highlights a holistic, integrated, and multi-disciplinary approach to design analysis of valve train systems, referred to as multi-physics. The analysis comprises various forms of physical phenomena and their interactions, including large displacement inertial dynamics, small amplitude oscillations due to system compliances, tribology, contact mechanics, and durability at the cam-tappet contact. Therefore, it also represents a multi-scale investigation, where the phenomena can be investigated at system level and referred back to underlying causes at subsystem or component level, in other words, implications of an event at microcosm can be ascertained on the overall system performance. This approach is often referred to in industry as down-cascading and up-cascading. The particular case reported here to outline the merits of this approach concerns a four-stroke single-cylinder engine. This promotes a system approach to engineering analysis for integrated noise, vibration, and harshness, durability and frictional assessment (efficiency). Experimental validation is provided with a motored test rig, using laser doppler vibrometry

Evidence for Excimer Photoexcitations in an Ordered {\pi}-Conjugated Polymer Film

We report pressure-dependent transient picosecond and continuous-wave photomodulation studies of disordered and ordered films of 2-methoxy-5-(2-ethylhexyloxy) poly(para-phenylenevinylene). Photoinduced absorption (PA) bands in the disordered film exhibit very weak pressure dependence and are assigned to intrachain excitons and polarons. In contrast, the ordered film exhibits two additional transient PA bands in the midinfrared that blueshift dramatically with pressure. Based on high-order configuration interaction calculations we ascribe the PA bands in the ordered film to excimers. Our work brings insight to the exciton binding energy in ordered films versus disordered films and solutions. The reduced exciton binding energy in ordered films is due to new energy states appearing below the continuum band threshold of the single strand.Comment: 5.5 pages, 5 figure