First-principles method of propagation of tightly bound excitons: exciton band structure of LiF and verification with inelastic x-ray scattering

We propose a simple first-principles method to describe propagation of tightly bound excitons. By viewing the exciton as a composite object (an effective Frenkel exciton in Wannier orbitals), we define an exciton kinetic kernel to encapsulate the exciton propagation and decay for all binding energy. Applied to prototypical LiF, our approach produces three exciton bands, which we verified quantitatively via inelastic x-ray scattering. The proposed real-space picture is computationally inexpensive and thus enables study of the full exciton dynamics, even in the presence of surfaces and impurity scattering. It also provides intuitive understanding to facilitate practical exciton engineering in semiconductors, strongly correlated oxides, and their nanostructures.Comment: 5 pages, 4 figures. Accepted by PR

Tourism, jobs, capital accumulation and the economy: A dynamic analysis

This paper examines the effects of tourism on labor employment, capital accumulation and resident welfare for a small open economy with unemployment. A tourism boom improves the terms of trade, increases labor employment, but lowers capital accumulation. The reduction in the capital stock depends on the degree of factor intensity. When the traded sector is weakly capital intensive, the fall in capital would not be so severe and the expansion of tourism improves welfare. However, when the traded sector is strongly capital intensive, the fall in capital can be a dominant factor to lower welfare. This immiserizing result of tourism on resident welfare is confirmed by the German data.tourism ; employment ; capital accumulation ; welfare

VI-Band Follow-Up Observations of Ultra-Long-Period Cepheid Candidates in M31

The ultra-long period Cepheids (ULPCs) are classical Cepheids with pulsation periods exceeding $\approx 80$ days. The intrinsic brightness of ULPCs are ~1 to ~3 mag brighter than their shorter period counterparts. This makes them attractive in future distance scale work to derive distances beyond the limit set by the shorter period Cepheids. We have initiated a program to search for ULPCs in M31, using the single-band data taken from the Palomar Transient Factory, and identified eight possible candidates. In this work, we presented the VI-band follow-up observations of these eight candidates. Based on our VI-band light curves of these candidates and their locations in the color-magnitude diagram and the Period-Wesenheit diagram, we verify two candidates as being truly ULPCs. The six other candidates are most likely other kinds of long-period variables. With the two confirmed M31 ULPCs, we tested the applicability of ULPCs in distance scale work by deriving the distance modulus of M31. It was found to be $\mu_{M31,ULPC}=24.30\pm0.76$ mag. The large error in the derived distance modulus, together with the large intrinsic dispersion of the Period-Wesenheit (PW) relation and the small number of ULPCs in a given host galaxy, means that the question of the suitability of ULPCs as standard candles is still open. Further work is needed to enlarge the sample of calibrating ULPCs and reduce the intrinsic dispersion of the PW relation before re-considering ULPCs as suitable distance indicators.Comment: 13 pages, with 14 Figures and 4 Tables (one online table). AJ accepte

Electronic spectra and photophysics of platinum(II) complexes with α-diimine ligands. Mixed complexes with halide ligands

Emission properties have been studied for a series of compounds of the formula (L_2)PtC1_2, where L_2 is N,N,N',N'-tetramethylethylenediamine, 2,2'-bipyridine (bpy), 4,4'-Me_2bpy, 5,5'-Me_2bpy, 4,4'-(t-Bu)_2bpy, 3,3'-(CH_3OCO)_2bpy, and 1,10-phenanthroline, and also for the compound Pt(bpy)I_2. Most of them exhibit orange to red luminescence from a triplet ligand-field (^3LF) state, both as solids and in glassy solution. These emissions are very broad (fwhm 2300-3400 cm^(-1) at 10 K) and structureless and are strongly Stokes-shifted from absorption. The two exceptions are the solid "red" form of Pt(bpy)Cl_2, which exhibits a relatively narrow (fwhm 1050 cm^(-1) at 10 K), vibronically structured (Δν ~ 1500 cm^-1)) red emission, and Pt(3,3'-(CH_3OCO)_2bpy)Cl_2, which exhibits a broad (fwhm 2500 cm^(-1) at 10 K) but structured (Δν ~1300 cm^(-1)) orange emission. Both of these emissions are assigned to triplet metal-to-ligand charge-transfer (^3MLCT) excited states. For the former compound, a linear-chain structure has destabilized a dσ*(d_(z^2)) level, yielding a dσ* → π*(bpy) state as the lowest energy excited state, while for the latter, the strongly electron-withdrawing substituents have stabilized a bpy π* level, yielding a dσ* → π*(bpy) state as the lowest energy excited state. The relative energies of the various types of excited states, including ligand 3_(ππ*) states, are discussed in detail. The crystal structures of Pt(5,5'-Me_2bpy)Cl_2 (monoclinic Cc, Z = 4, a = 13.413(7) Å, b = 9.063(4) Å, c = 12.261(9) Å, 0 = 121.71(6)') and Pt(3,3'-(CH_3OCO)_2bpy)Cl_2 (triclinic P1, Z = 2, a = 7.288(2) Å, b = 9.932(3) Å, c = 11.881(5) Å, α = 98.04(3)°, β = 103.56(3)°, γ = 106.54(3)°) are reported

Comparative study of visible light polymerized gelatin hydrogels for 3D culture of hepatic progenitor cells

Photopolymerization techniques have been widely used to create hydrogels for biomedical applications. Visible light-based photopolymerizations are commonly initiated by type II (i.e., noncleavage-type) photoinitiator in conjunction with a coinitiator. On the other hand, type I photoinitiators (i.e., cleavage type) are rarely compatible with visible light-based initiation due to their limited molar absorbability in the visible light wavelengths. Here, we report visible light initiated orthogonal photoclick crosslinking to fabricate gelatin-norbornene and poly(ethylene glycol)-tetra-thiol hydrogels using either cleavage-type (i.e., lithium acylphosphinate, LAP) or noncleavage-type photoinitiator (i.e., eosin-Y, EY) without the use of a coinitiator. Regardless of the initiator type, the step-growth gelatin-PEG hybrid hydrogels crosslinked and degraded similarly. While both systems exhibited similar cytocompatibility for hepatic progenitor HepaRG cells, gelation initiated by noncleavage-type initiator EY afforded slightly higher degree of hepatic gene expression

Chemoenzymatic elaboration of monosaccharides using engineered cytochrome P450_(BM3) demethylases

Polysaccharides comprise an extremely important class of biopolymers that play critical roles in a wide range of biological processes, but the synthesis of these compounds is challenging because of their complex structures. We have developed a chemoenzymatic method for regioselective deprotection of monosaccharide substrates using engineered Bacillus megaterium cytochrome P450 (P450_(BM3)) demethylases that provides a highly efficient means to access valuable intermediates, which can be converted to a wide range of substituted monosaccharides and polysaccharides. Demethylases displaying high levels of regioselectivity toward a number of protected monosaccharides were identified using a combination of protein and substrate engineering, suggesting that this approach ultimately could be used in the synthesis of a wide range of substituted mono- and polysaccharides for studies in chemistry, biology, and medicine

Preparation of GHZ states via Grover's quantum searching algorithm

In this paper we propose an approach to prepare GHZ states of an arbitrary multi-particle system in terms of Grover's fast quantum searching algorithm. This approach can be regarded as an extension of the Grover's algorithm to find one or more items in an unsorted database.Comment: 9 pages, Email address: [email protected]

Convergent diversity-oriented side-chain macrocyclization scan for unprotected polypeptides

Here we describe a general synthetic platform for side-chain macrocyclization of an unprotected peptide library based on the S[subscript N]Ar reaction between cysteine thiolates and a new generation of highly reactive perfluoroaromatic small molecule linkers. This strategy enabled us to simultaneously “scan” two cysteine residues positioned from i, i + 1 to i, i + 14 sites in a polypeptide, producing 98 macrocyclic products from reactions of 14 peptides with 7 linkers. A complementary reverse strategy was developed; cysteine residues within the polypeptide were first modified with non-bridging perfluoroaryl moieties and then commercially available dithiol linkers were used for macrocyclization. The highly convergent, site-independent, and modular nature of these two strategies coupled with the unique chemoselectivity of a S[subscript N]Ar transformation allows for the rapid diversity-oriented synthesis of hybrid macrocyclic peptide libraries with varied chemical and structural complexities.National Institutes of Health (U.S.) (GM101762)National Institutes of Health (U.S.) (GM046059)MIT Faculty Start-up FundSontag Foundation (Distinguished Scientist Award)Deshpande Center for Technological InnovationMassachusetts Institute of Technology (Charles E. Reed Faculty Initiative Fund)Damon Runyon Cancer Research Foundatio

Electron doping evolution of the neutron spin resonance in NaFe1−x_{1-x}Cox_{x}As

Neutron spin resonance, a collective magnetic excitation coupled to superconductivity, is one of the most prominent features shared by a broad family of unconventional superconductors including copper oxides, iron pnictides, and heavy fermions. In this work, we study the doping evolution of the resonances in NaFe$_{1-x}$Co$_x$As covering the entire superconducting dome. For the underdoped compositions, two resonance modes coexist. As doping increases, the low-energy resonance gradually loses its spectral weight to the high-energy one but remains at the same energy. By contrast, in the overdoped regime we only find one single resonance, which acquires a broader width in both energy and momentum, but retains approximately the same peak position even when $T_c$ drops by nearly a half compared to optimal doping. These results suggest that the energy of the resonance in electron overdoped NaFe$_{1-x}$Co$_x$As is neither simply proportional to $T_c$ nor the superconducting gap, but is controlled by the multi-orbital character of the system and doped impurity scattering effect.Comment: accepted by PR