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A single photoexcited electron-hole pair within a polar semiconductor nanocrystal (SNC) alters the charge screening and shielding within it. Perturbations of the crystal lattice and of the valence and conduction bands result, and the quantum-confinement states in a SNC shift uniquely with a dependence on the states occupied by the carriers. This shifting is termed quantum-state renormalization (QSR). This Perspective highlights QSR in semiconductor quantum wires and dots identified in time-resolved transient absorption and two-dimensional electronic spectroscopy experiments. Beyond the interest in understanding the principles of QSR and energy-coupling mechanisms, we pose the contributions of QSR in time-resolved spectroscopy data must be accounted for to accurately identify the time scales for intraband relaxation of the carriers within SNCs.

Polycyclic aromatic hydrocarbons (PAHs) are organic molecules containing adjacent aromatic rings. Infrared emission bands show that PAHs are abundant in space, but only a few specific PAHs have been detected in the interstellar medium. We detected 1-cyanopyrene, a cyano-substituted derivative of the related four-ring PAH pyrene, in radio observations of the dense cloud TMC-1, using the Green Bank Telescope. The measured column density of 1-cyanopyrene is [Formula: see text] cm -2 , from which we estimate that pyrene contains up to 0.1% of the carbon in TMC-1. This abundance indicates that interstellar PAH chemistry favors the production of pyrene. We suggest that some of the carbon supplied to young planetary systems is carried by PAHs that originate in cold molecular clouds.

Ion time-of-flight velocity-map imaging was used to measure the kinetic-energy distributions of the I2 ion-pair fragments formed after photoexcitation of Ar⋯I2 complexes to intermolecular vibrational levels bound within the Ar + I2 (E, vE = 0-2) potential energy surfaces. The kinetic-energy distributions of the I2 products indicate that complexes in the Ar⋯I2 (E, vE) levels preferentially dissociate into I2 in the D and β ion-pair states with no change in I2 vibrational excitation. The energetics of the levels prepared suggest that there is a non-adiabatic coupling of the initially prepared levels with the continuum of states lying above the Ar + I2 (D, vD = vE) and Ar + I2 (β, vβ = vE) dissociation limits. The angular anisotropies of the I2 product signals collected for many of the Ar⋯I2 (E, vE) levels have maxima parallel to the laser polarization axis. This contradicts expectations for the prompt dissociation of complexes with T-shaped geometries, which would result in images with maxima perpendicular to the polarization axis. These anisotropies suggest that there is a perturbation of the transition moment in these clusters or there are additional intermolecular interactions, likely those sampled while traversing above the attractive wells of the lower-energy potentials during dissociation. I2 (D', vD') products are also identified when preparing several of the low-lying levels localized in the T-shaped well of the Ar + I2 (E, vE = 0-2) potentials, and they are formed in multiple νD' vibrational levels spanning energy ranges up to 500 cm-1., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

The vibrational predissociation dynamics of H 2 /D 2 ···I 35 Cl(B, v '=3) complexes containing both para - and ortho -hydrogen prepared in different intermolecular vibrational levels were investigated. The Δ v = -1 I 35 Cl(B, v = 2, j ) rotational product-state distributions measured for excitation to the lowest-energy T-shaped levels of these complexes are mostly bimodal. The rotational distributions measured for excitation of the H 2 ···I 35 Cl(B, v '=3) complexes are colder than those of the D 2 ···I 35 Cl(B, v '=3) complexes, and there are only slight differences between those measured for the para - and ortho -hydrogen containing complexes. Excitation of the delocalized bending levels results in slightly colder rotational product-state distributions. The distributions suggest the dynamics result from more than impulsive dissociation off of the inner repulsive wall of the lower-energy H 2 /D 2 + I 35 Cl(B, v = 2) potential surfaces of the products. The depths of these potentials and the energies available to these products also contribute to the dynamics. The formation of the Δ v = -2, I 35 Cl(B, v = 1) product channel was only identified for excitation of levels within the ortho ( j = 0)-D 2 + I 35 Cl(B, v '=3) potential. The formation of this channel occurs via I 35 Cl(B, v '=3) vibrational to D 2 rotational energy transfer forming the ortho ( j = 2)-D 2 + I 35 Cl(B, v = 1, j ) products.

We have conducted an extensive search for nitrogen-, oxygen-, and sulfur-bearing heterocycles toward Taurus Molecular Cloud 1 (TMC-1) using the deep, broadband centimeter-wavelength spectral line survey of the region from the GOTHAM large project on the Green Bank Telescope. Despite their ubiquity in terrestrial chemistry, and the confirmed presence of a number of cyclic and polycyclic hydrocarbon species in the source, we find no evidence for the presence of any heterocyclic species. Here, we report the derived upper limits on the column densities of these molecules obtained by Markov Chain Monte Carlo (MCMC) analysis and compare this approach to traditional single-line upper limit measurements. We further hypothesize why these molecules are absent in our data, how they might form in interstellar space, and the nature of observations that would be needed to secure their detection.

Wurtzite CdSe quantum belts with L-type n -octylamine, L-type ammonia, or Z-type Cd(oleate) 2 ligands are exchanged for several metal-dithiocarbamate ligands [M(S 2 CNR 1 R 2 ) 2 ]: Cd(S 2 CNPhMe) 2 , Cd(S 2 CNEt 2 ) 2 , Zn(S 2 CNPhMe) 2 , and Zn(S 2 CNEt 2 ) 2 . Successful ligand exchange with all M(S 2 CNR 1 R 2 ) 2 compounds occurs from {CdSe[Cd(oleate) 2 ] 0.19 } quantum belts (QBs), which induce similar spectral shifts in the absorption spectra of the ligand-exchanged QBs. Spectroscopic data, experimentally determined lattice strains, and ligand exchanges with [Na][Et 2 NCS 2 ] and [NH 4 ][MePhNCS 2 ] establish that the [M(S 2 CNR 1 R 2 ) 2 ] ligands bind as bound-ion-paired X-type ligands with (S 2 CNR 1 R 2 ) - groups ligated directly to the QB surfaces and [M(S 2 CNR 1 R 2 )] + groups serving as the charge-balancing ion-paired countercations. The X-type dithiocarbamate ligands do not impart any special electronic effects to the CdSe QBs.

Bipyridiniums, also known as viologens, are well-documented electron acceptors that are generally easy to synthesize on a large scale and reversibly cycle between three oxidation states (V 2+ , V •+ , and V 0 ). Accordingly, they have been explored in a number of applications that capitalize on their dynamic redox chemistry, such as redox-flow batteries and electrochromic devices. Viologens are also particularly useful in photoinduced electron transfer (PET) processes and therefore are of interest in photovoltaic applications that typically rely on electron-rich donors like polythiophene (PTh). However, the PET mechanism and relaxation dynamics between interfacing PTh and viologen-based thin films has not been well studied as a function of thickness of the acceptor layer. Here, a novel, bilayered thin film composite was fabricated by first spin-coating PTh onto glass slides, followed by spin-coating and curing polyviologen (PV)-based micron-sized films of variable thicknesses (0.5-11.3 μm) on top of the PTh layer. The electron-transfer mechanism and relaxation dynamics from the PTh sublayer into the upper PV film were investigated using femtosecond transient absorption (fTA) spectroscopy and electrochemistry to better understand how the charge-transfer/relaxation lifetimes could be extended using thicker PV acceptor films. The fTA experiments were performed under inert N 2 conditions as well as in ambient O 2 . The latter shortened the lifetimes of the electrons in the PV layer, presumably due to O 2 triplet-based trap sites. Contact angle measurements using H 2 O and MeI were also performed on top of the bilayered films to measure changes in surface free energy that would aid the assessment related to efficiency of the combined processes involving light penetration, photoexcitation, electron mobility, and relaxation from within the bilayered thin films. Insights gained from this work will support the development of future devices that employ viologen-based materials as an alternative electron-acceptor that is both easily processable and scalable., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The competition between multiple pathways sampled during the energetic relaxation of excited molecules can be difficult to experimentally decipher. The rare gas···dihalogen van der Waals complexes have remained key systems for exploring the competition between relaxation pathways, such as intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP). As these mechanisms can yield the same products, the relaxation pathways traversed are often deduced from the excitation spectra or product-state distributions. In addition to a brief perspective on IVR and VP in rare gas⋯dihalogen complexes, we present new results obtained using time-of-flight velocity-map imaging (VMI) on T-shaped Ar⋯I 2 (B, ν ', n ' = 0) complexes that illustrate how contributions from these two pathways can be separated. The angular anisotropies of the ion images collected for the I 2 (B, ν < ν ') fragments indicate the products for certain Ar⋯I 2 (B, ν ', n ' = 0) levels are weighted along the direction perpendicular to the laser-polarization axis. These distributions are consistent with prompt dissociation of the T-shaped excited-state complexes, likely via direct VP. The distributions measured for other Ar⋯I 2 (B, ν ', n ' = 0) levels are preferentially along the laser-polarization axis. These initially prepared levels must undergo IVR with nearly resonant Ar⋯I 2 (B, ν < ν ', n > 0) intermolecular vibrational levels that sample linear Ar-I-I orientations during dissociation.

Unidentified infrared emission bands are ubiquitous in many astronomical sources. These bands are widely, if not unanimously, attributed to collective emissions from polycyclic aromatic hydrocarbon (PAH) molecules, yet no single species of this class has been identified in space. Using spectral matched filtering of radio data from the Green Bank Telescope, we detected two nitrile-group-functionalized PAHs, 1- and 2-cyanonaphthalene, in the interstellar medium. Both bicyclic ring molecules were observed in the TMC-1 molecular cloud. In this paper, we discuss potential in situ gas-phase PAH formation pathways from smaller organic precursor molecules., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

The state-to-state intraband relaxation dynamics of charge carriers photogenerated within CdTe quantum wires (QWs) are characterized via transient absorption spectroscopy. Overlapping signals from the energetic-shifting of the quantum-confinement features and the occupancy of carriers in the states associated with these features are separated using the quantum-state renormalization model. Holes generated with an excitation energy of 2.75 eV reach the band edge within the instrument response of the measurement, ∼200 fs. This extremely short relaxation time is consistent with the low photoluminescence quantum yield of the QWs, ∼0.2%, and the presence of alternative relaxation pathways for the holes. The electrons relax through the different energetically available quantum-confinement states, likely via phonon coupling, with an overall rate of ∼0.6 eV ps -1 .

The excitation energy dependence (EED) of the photoluminescence quantum yield (Φ PL ) of semiconductor nanoparticles with varying dimensionalities is reported. Specifically, the EEDs of CdSe quantum dots, CdSe quantum platelets, CdSe quantum belts, and CdTe quantum wires were determined via measurements of individual Φ PL values and photoluminescence efficiency (PL Eff ( E )) spectra. There is a general trend of overall decreasing efficiency for radiative recombination with increasing excitation energy. In addition, there are often local minima in the PL Eff ( E ) spectra that are most often at energies between quantum-confinement transitions. The average PL lifetimes of the samples do not depend on the excitation energy, suggesting that the EED of Φ PL arises from charge carrier trapping that competes efficiently with intraband carrier relaxation to the band edge. The local minima in the PL Eff ( E ) spectra are attributed to excitation into optically coupled states that results in the loss of carriers in the semiconductor. The EED data suggest that the PL Eff ( E ) spectra depend on the sample synthesis, preparation, surface passivation, and environment.

The role of electronic predissociation (EP) in the dissociation dynamics of rare gas⋯dihalogen complexes (Rg⋯X 2 ) prepared in the B electronic state was probed using ion time-of-flight velocity-map imaging. Specifically, EP of complexes prepared in the T-shaped Ar⋯I 2 , Ne⋯I 2 , He⋯I 2 , Ar⋯Br 2 , Ne⋯Br 2 , and He⋯Br 2 levels with varying amounts of X 2 vibrational excitation, ν', was investigated. The atomic I( 2 P 3/2 ) or Br( 2 P 3/2 ) EP fragments were probed using ion time-of-flight velocity-map imaging. Definitive evidence for EP was observed only for the Ar⋯I 2 complex, and it occurs for all of the T-shaped intermolecular levels investigated, those with ν' = 12-22, 24, and 25. The relative yields for EP in these levels measured as a function of ν' are consistent with previously reported yields for the competing mechanism of vibrational predissociation. The anisotropies of the I + images collected for Ar⋯I 2 indicate that EP is occurring on timescales shorter than the rotational periods of the complex. The kinetic energy distributions of the departing I-atom fragments suggest that EP occurs from an asymmetric geometry rather than the rigid T-shaped geometry for many of the Ar⋯I 2 levels prepared. These findings indicate that intramolecular vibrational redistribution of these initially prepared T-shaped levels to excited levels bound within a lower-energy intermolecular potential occurs prior to EP.

The synthesis of epitaxial CdSe/PbS core/shell quantum dots (QDs) is reported. The PbS shell grows in a rock salt structure on the zinc blende CdSe core, thereby creating a crystal structure mismatch through additive growth. Absorption and photoluminescence (PL) band edge features shift to lower energies with increasing shell thickness, but remain above the CdSe bulk band gap. Nevertheless, the profiles of the absorption spectra vary with shell growth, indicating that the overlap of the electron and hole wave functions is changing significantly. This leads to over an order of magnitude reduction of absorption near the band gap and a large, tunable energy shift, of up to 550 meV, between the onset of strong absorption and the band edge PL. While the bulk valence and conduction bands adopt an inverse type-I alignment, the observed spectroscopic behavior is consistent with a transition between quasi-type-I and quasi-type-II behavior depending on shell thickness. Three effective mass approximation models support this hypothesis and suggest that the large difference in effective masses between the core and shell results in hole localization in the CdSe core and a delocalization of the electron across the entire QD. These results show the tuning of wave functions and transition energies in CdSe/PbS nanoheterostructures with prospects for use in optoelectronic devices for luminescent solar concentration or multiexciton generation.

Cadmium bis(phenyldithiocarbamate) [Cd(PTC) 2 ] is prepared and structurally characterized. The compound crystallizes in the monoclinic space group P2 1 /n. A one-dimensional polymeric structure is adopted in the solid state, having bridging PTC ligands and 6-coordinate pseudo-octahedral Cd atoms. The compound is soluble in DMSO, THF, and DMF and insoluble in EtOH, MeOH, CHCl 3 , CH 2 Cl 2 , and toluene. {CdSe[n-octylamine] 0.53 } quantum belts and Cd(PTC) 2 react to deposit epitaxial CdS shells on the nanocrystals. With an excess of Cd(PTC) 2 , the resulting thick shells contain spiny CdS nodules grown in the Stranski-Krastanov mode. Stoichiometric control affords smooth, monolayer CdS shells. A base-catalyzed reaction pathway is elucidated for the conversion of Cd(PTC) 2 to CdS, which includes phenylisothiocyanate and aniline as intermediates, and 1,3-diphenylthiourea as a final product.

We report ensemble extinction and photoluminesence spectra for colloidal CdTe quantum wires (QWs) with nearly phase-pure, defect-free wurtzite (WZ) structure, having spectral line widths comparable to the best ensemble or single quantum-dot values, to the single polytypic (having WZ and zinc blende (ZB) alternations) QW values, and to those of two-dimensional quantum belts or platelets. The electronic structures determined from the multifeatured extinction spectra are in excellent agreement with the theoretical results of WZ QWs having the same crystallographic orientation. Optical properties of polytypic QWs of like diameter and diameter distribution are provided for comparison, which exhibit smaller bandgaps and broader spectral line widths. The nonperiodic WZ-ZB alternations are found to generate non-negligible shifts of the bandgap to intermediate energies between the quantum-confined WZ and ZB energies. The alternations and variations in the domain sizes result in inhomogeneous spectral line width broadening that may be more significant than that arising from the 12-13% diameter distributions within the QW ensembles.

Life on Earth relies on chiral molecules-that is, species not superimposable on their mirror images. This manifests itself in the selection of a single molecular handedness, or homochirality, across the biosphere. We present the astronomical detection of a chiral molecule, propylene oxide (CH3CHCH2O), in absorption toward the Galactic center. Propylene oxide is detected in the gas phase in a cold, extended molecular shell around the embedded, massive protostellar clusters in the Sagittarius B2 star-forming region. This material is representative of the earliest stage of solar system evolution in which a chiral molecule has been found., (Copyright © 2016, American Association for the Advancement of Science.)

CuInS2 nanocrystals are prepared by ion exchange with template Cu2-xS nanoplatelets and InX3 [X = chloride, iodide, acetate (OAc), or acetylacetonate (acac)]. The morphologies of the resultant nanocrystals depend on the InX3 precursor and the reaction temperature. Exchange with InCl3 at 150 °C produces CuInS2 nanoplatelets having central holes and thickness variations, whereas the exchange at 200 °C produces intact CuInS2 nanoplatelets in which the initial morphology is preserved. Exchange with InI3 at 150 °C produces CuInS2 nanoplatelets in which the central hollowing is more extreme, whereas exchange with In(OAc)3 or In(acac)3 at 150 °C produces intact CuInS2 nanoplatelets. The results establish that the ion exchange occurs through the thin nanoplatelet edge facets. The hollowing and hole formation are due to a nanoscale Kirkendall Effect operating in the reaction-limited regime for displacement of X(-) at the edges, to allow insertion of In(3+) into the template nanoplatelets.

CONSPECTUS: Semiconductor nanocrystals having an extended length dimension and capable of efficiently transporting energy and charge would have useful applications in solar-energy conversion and other emerging technologies. Pseudocylindrical semiconductor nanowires and quantum wires are available that could potentially serve in this role. Sadly, however, their defective surfaces contain significant populations of surface trap sites that preclude efficient transport. The very large surface area of long wires is at least part of the problem. As electrons, holes, and excitons migrate along a nanowire or quantum wire, they are exposed to an extensive surface and to potentially large numbers of trap sites. A solution to this dilemma might be found by identifying "long" semiconductor nanocrystals of other morphologies that are better passivated. In this Account, we discuss a newly emerging family of flat semiconductor nanocrystals that have surprising characteristics. These thin, flat nanocrystals have up to micrometer-scale (orthogonal) lateral dimensions and thus very large surface areas. Even so, their typical photoluminescence efficiencies of 30% are astonishingly high and are 2 orders of magnitude higher than those typical of semiconductor quantum wires. The very sharp emission spectra of the pseudo-two-dimensional nanocrystals reflect a remarkable uniformity in their discrete thicknesses. Evidence that excitons are effectively delocalized and hence transported over the full dimensions of these nanocrystals has been obtained. The excellent optical properties of the flat semiconductor nanocrystals confirm that they are exceptionally well passivated. This Account summarizes the two synthetic methods that have been developed for the preparation of pseudo-two-dimensional semiconductor nanocrystals. A discussion of their structural features accounts for their discrete, uniform thicknesses and details the crystal-lattice expansions and contractions they exhibit. An analysis of their optical properties justifies the sharp photoluminescence spectra and high photoluminescence efficiencies. Finally, a bilayer mesophase template pathway is elucidated for the formation of the nanocrystals, explaining their flat morphologies. Magic-size nanocluster intermediates are found to be potent nanocrystal nucleants, allowing the synthesis temperatures to be decreased to as low as room temperature. The potential of these flat semiconductor nanocrystals in the form of nanoribbons or nanosheets for long-range energy and charge transport appears to be high.

Reaction of Cd(OAc) 2 ·2H 2 O and selenourea in primary-amine/secondary-amine cosolvent mixtures affords crystalline CdSe quantum platelets at room temperature. Their crystallinity is established by X-ray diffraction analysis (XRD), high-resolution transmission electron microscopy (TEM), and their sharp extinction and photoluminescence spectra. Reaction monitoring establishes the magic-size nanocluster (CdSe) 34 to be a key intermediate in the growth process, which converts to CdSe quantum platelets by first-order kinetics with no induction period. The results are interpreted to indicate that the critical crystal-nucleus size for CdSe under these conditions is in the range of (CdSe) 34 to (CdSe) 68 . The nanocluster is obtained in isolated form as [(CdSe) 34 ( n -octylamine) 16 (di- n -pentylamine) 2 ], which is proposed to function as crystal nuclei that may be stored in a bottle.

The photoluminescence (PL) intensity of semiconductor quantum dots (QDs) is routinely monitored to track the chemical and physical properties within a sample or device incorporating the QDs. A dependence of the PL quantum yields (QYs) on the excitation energy could lead to erroneous conclusions but is commonly not considered. We summarize previous evidence and present results from two methodologies that confirm the possibility of a dependence of the PL QYs on the excitation energy. The data presented indicate that PL QYs of CdSe and CdSe/ZnS QDs suspended in toluene are highest for excitation just above the band gap, Eg, of each. The PL QYs decrease with increasing excitation energies up to 1 eV above Eg. The PL intensity decay profiles recorded for these samples at varying emission and excitation energies indicate that the changes in the PL QYs result from the nonradiative relaxation pathways sampled as the charge carriers relax down to the band edge.

Colloidal CdTe quantum wires are reported having ensemble photoluminescence efficiencies as high as 25% under low excitation-power densities. High photoluminescence efficiencies are achieved by formation of a monolayer CdS shell on the CdTe quantum wires. Like other semiconductor nanowires, the CdTe quantum wires may contain frequent wurtzite-zinc-blende structural alternations along their lengths. The present results demonstrate that the optical properties, emission-peak shape and photoluminescence efficiencies, are independent of the presence or absence of such structural alternations.

Photogenerated electron-hole pairs are observed to be bound as 1D excitons in CdSe quantum wires (QWs) at room temperature. Microscopy experiments performed on dilute samples of CdSe QWs prepared on coverslips with patterned electrodes reveal that there is no change in either the overall photoluminescence (PL) intensity or the distribution of the PL intensity with the application of an external electric field. Changes in the PL intensity, and thus evidence for separate charge carriers within the QWs, are observed only for concentrated samples. In these concentrated samples, a thin film of other compounds, including trioctylphosphine oxide and a bismuth salt formed in the synthesis, is observed to encompass the QWs. The separate charge carriers that influence the PL intensity are attributed to the other compounds in the sample.

Two-laser, action spectroscopy experiments have been performed in the I(2)B-X, υ'-0 spectral region on H(2)···I(2) and D(2)···I(2) complexes to investigate the dependence of the H(2)/D(2) + I(2) intermolecular interactions on orientation. The spectra contain features associated with at least two different conformers of the ground-state H(2)/D(2)···I(2)(X,υ'' = 0) complexes; one conformer has a preferred T-shaped geometry with the H(2)/D(2) moiety localized in a potential minimum that is orthogonal to the I-I bond axis, and the second conformer has a linear geometry with the H(2)/D(2) moiety positioned in minima at either end of the I(2) molecule, along the bond axis. Those features associated with complexes containing para-H(2)(j = 0), ortho-H(2)(j = 1), ortho-D(2)(j = 0), and para-D(2)(j = 1) are also assigned. The linear conformers are found to be more strongly bound than the T-shaped conformers with binding energies of 118.9(1.9) cm(-1) versus 91.3-93.3 cm(-1) for the ortho-H(2)···I(2) complexes and 144.2(2.1) cm(-1) versus 107.9 cm(-1) for the para-D(2)···I(2) complexes, respectively. Electronic structure calculations of the complexes containing ICl and I(2) with H(2), He, Ne, and Ar were performed to reveal the nature of the interactions and to shed insight into the origins of the different binding energies. The most stable minima in the H(2)/D(2) + I(2)(B,υ') excited-state potentials have T-shaped geometries. Calculated energies and probability amplitudes of the excited-state levels provide insight into the different excited-state intermolecular vibrational levels accessed by transitions of the two ground-state conformers.

We report the growth of cadmium-selenide (CdSe) quantum-wire (QW) films on a variety of substrates by the solution-liquid-solid (SLS) method. Our SLS syntheses employ size-controlled, near-monodisperse bismuth (Bi) nanoparticles (NPs) as the catalysts for QW growth, which offers several advantages over Bi NPs thermally generated from thin Bi films, including mean QW diameter control, narrow diameter distributions, small diameters in the quantum-confinement regime, and control of the QW density on the substrates. The Bi NPs are deposited on the substrates via drop casting of a Bi-NP solution and subsequently annealed in a reducing atmosphere, a key step to ensure firm attachment of the Bi NPs onto the substrates and maintenance of their catalytic activity for the QW-film growth. The QW growth density is proportional to the Bi-NP coating density, which is determined by the concentration of the Bi-NP deposition solution. Lower concentrations are used for small Bi NPs to reduce their high tendency for agglomeration and to achieve control over mean QW diameter and to produce narrow diameter distributions. Spectroscopic evidence of quantum confinement is provided. Related films of InP, InAs, and PbSe QWs are also described.

The Fenna-Matthews-Olson light-harvesting antenna (FMO) protein has been a model system for understanding pigment-protein interactions in the energy transfer process in photosynthesis. All previous studies have utilized wild-type FMO proteins from several species. Here we report the purification and characterization of the first FMO protein variant generated via replacement of the esterifying alcohol at the C-17 propionate residue of bacteriochlorophyll (BChl) a, phytol, with geranylgeraniol, which possesses three more double bonds. The FMO protein still assembles with the modified pigment, but both the whole cell absorption and the biochemical purification indicate that the mutant cells contain a much less mature FMO protein. The gene expression was checked using qRT-PCR, and none of the genes encoding BChl a-binding proteins are strongly regulated at the transcriptional level. The smaller amount of the FMO protein in the mutant cell is probably due to the degradation of the apo-FMO protein at different stages after it does not bind the normal pigment. The absorption, fluorescence, and CD spectra of the purified FMO variant protein are similar to those of the wild-type FMO protein except the conformations of most pigments are more heterogeneous, which broadens the spectral bands. Interestingly, the lowest-energy pigment binding site seems to be unchanged and is the only peak that can be well resolved in 77 K absorption spectra. The excited-state lifetime of the variant FMO protein is unchanged from that of the wild type and shows a temperature-dependent modulation similar to that of the wild type. The variant FMO protein is less thermally stable than the wild type. The assembly of the FMO protein and also the implications of the decreased FMO/chlorosome stoichiometry are discussed in terms of the topology of these two antennas on the cytoplasmic membrane.

CdSe quantum belts (QBs) having lengths of 0.5-1.5 microm and thicknesses of 1.5-2.0 nm exhibit high photoluminescence (PL) efficiencies of approximately 30%. Epifluorescence studies establish the PL spectra to be uniform along single QBs, and nearly the same from QB to QB. Photogenerated excitons are shown to be effectively delocalized over the entire QBs by position-selective excitation. Decoration of the QBs with gold nanoparticles indicates a low density of surface-trap sites, located primarily on the thin belt edges. The high PL efficiencies and effective exciton delocalization are attributed to the minimization of defective {1100} edge surface area or edge-top/bottom (face) line junctions in QBs relative to quantum wires having roughly isotropic cross sections, for which very low PL quantum efficiencies have been reported. The results suggest that trap sites can be minimized in pseudo-one-dimensional nanocrystals, such that the facile transport of energy and charge along their long axes becomes possible.

Photodissociation of the Ar-I(2) 1:1 linear van der Waals complex is studied over the 490-520 nm region using the velocity-map imaging technique. Molecular iodine, and both the T-shaped and linear Ar-I(2)(X,v(")=0) ground-state complexes absorb strongly in this range, and these transitions access both the bound and dissociative regions of the I(2)(B) state. We measure the angle-speed distribution of vibrationally excited I(2)(B,v(')) state products by resonant 1+1 ionization via the E and f ion-pair states, forming I(2) (+), which is imaged under velocity-mapping conditions. The images show a strong angular anisotropy, which is the same for all excitation energies, spanning from the bound region to above the molecular dissociation limit. The observed angular anisotropy of the I(2) fragments is consistent with a direct dissociation of linear Ar-I(2) complexes promoted to the inner repulsive potential wall of the Ar+I(2)(B,v(')) potential energy surface.

Rovibronic transitions of multiple conformers of the He(2)...(79)Br(2)(X, v'' = 0), He(3)...(79)Br(2)(X, v'' = 0), He(2)...I(35)Cl(X, v'' = 0), and He(3)...I(35)Cl(X, v'' = 0) complexes stabilized in a pulsed, supersonic expansion are observed in action spectra recorded in the B-X region of the dihalogens. In addition to features associated with He(2)...(79)Br(2) and He(2)...I(35)Cl complexes with the rare gas atoms localized in the toroidal potential well lying in a plane perpendicular to the dihalogen bond, those associated with a ground-state conformer that has one He atom localized in the toroidal potential and the other He atom localized in the linear well at the end of the dihalogen moiety are also identified. Transitions of at least three conformers of the He(3)...Br(2) complex and two conformers of the He(3)...ICl complex are also observed. The relative populations of the different conformers are found to depend on where along the supersonic expansion the spectra are recorded, and thus on the local temperature regime sampled. The He(2)...(79)Br(2) and He(2)...I(35)Cl conformers with one He atom in each well are found to be the more stable conformers.

Resonant two-photon excitation of the T-shaped and linear He...I(35)Cl(X,v(") = 0) complexes is used to access the intermolecular vibrational levels bound within the He + ICl(beta,v(dagger) = 0-2) and He + ICl(E,v(dagger) = 11,12) intermolecular potentials. The excitation utilizes different metastable intermolecular vibrational levels within the He + ICl(A,v(') = 15) and He + ICl(B,v(') = 2,3) potentials to access levels with varying intermolecular vibrational excitation in the ion-pair states. In addition to providing data revealing properties of the He + ICl(E,v(dagger)) and He + ICl(beta,v(dagger)) potentials, the transition energies of the observed features permit the relative binding energies of the T-shaped and linear ground-state He...ICl(X,v(") = 0) conformers to be accurately measured. The binding energies of the T-shaped and linear He...I(35)Cl(X,v(") = 0) conformers are 16.6(3) and 22.0(2) cm(-1), respectively. These values and the observed transition energies are then used to set the binding energies of the T-shaped He...I(35)Cl complexes in the He + ICl(A,v(') = 15), He + ICl(B,v(') = 3), He + ICl(beta,v(dagger) = 1), and He + ICl(E,v(dagger) = 12) potentials as 13.4(3), 13.3(3), 41(1), and 39.2(4) cm(-1), respectively. Nonadiabatic coupling between specific intermolecular vibrational levels within the He + ICl(beta,v(dagger)) state and the ICl(D('),v(dagger)) molecular state is observed.

Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the D2...ICl van der Waals complex for both ortho-D2 (o-D2) and para-D2 (p-D2). As with the analogous H2...ICl van der Waals complexes [Darr, J. P.; Crowther, A. C.; Loomis, R. A.; Ray, S. E.; McCoy, A. B. J. Phys. Chem. A 2007, 111, 13387], the C2v conformer with the deuterium molecule localized at the iodine atom end of the dihalogen is significantly more stable than the asymmetric conformer that has the deuterium positioned orthogonally to the ICl bond axis, D0'' = 223.9(2.4) versus 97.3(8)-103.9(3) cm(-1) for p-D2...I(35)Cl(X, v''=0). For both conformers, complexes containing p-D2 are found to be more strongly bound than those with o-D2. The electronically excited D2...ICl(A, v') and D2...ICl(B, v') complexes are found to have equilibrium geometries that are nearly the same as those of the ground-state asymmetric structures. Calculated D2...ICl(B, v'=3) energies and probability amplitudes obtained using a simple scaled He + ICl(B, v'=3) potential provide clues to the nature of the different excited-state levels accessed.

The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,p-H2...I35,37Cl(X,v' '=0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D0' ' = 186.4(3) cm-1 versus 82.8(3)

Photoluminescence microscopy studies have detected synchronous-photoluminescence-intensity fluctuations along entire cadmium selenide quantum wires under continuous illumination. While similar photoluminescence blinking has been reported previously for semiconductor quantum dots and rods, the observation of synchronous blinking spanning the entire length of quantum wires, with diameters approximately 9 nm and lengths >5 microm, is remarkable. We propose a mechanism to account for the synchronous blinking that is based on a dynamic, photolytic filling of surface-trap sites.

The laser-induced fluorescence and action spectra of I2 in a helium supersonic expansion have been recorded in the I2 B-X, 20-0 region. Two features are identified within the spectra. The lower-energy feature arises from transitions between states that are localized in a T-shaped conformation on both the X- and B-state potentials. The higher-energy feature reflects transitions from states that are localized in a linear conformation on the X state to states that have energies that are larger than the barrier for free rotation of the rare gas atom about the I2 molecule on the B-state potential. Ground-state binding energies of 16.6(6) and 16.3(6) cm-1 were determined for the T-shaped and linear conformers, respectively. These spectra are compared to those calculated using the experimentally determined rotational temperatures. Based on the agreement between the experimental and calculated spectra, the binding energies of the J'=0 states with 0 and 2-6 quanta of excitation in the He...I2 bending mode on the B state were determined. Several models for the B-state potential were used to investigate the origins of the shape of the contour of the higher-energy feature in the spectra for He...I2 and He...Br2. The shape of the contours was found to be relatively insensitive to the choice of potential. This leads us to believe that the spectra of these systems are relatively insensitive to the parameters of the B-state potential energy surface and are more sensitive to properties of the halogen molecule.

Using laser-induced fluorescence and two-laser, pump-probe spectroscopy, collision-induced vibrational relaxation is observed to compete with the dissociation of electronically excited ICl in a helium carrier gas expansion. By thoroughly characterizing the expansion properties, we observe that collisions of ICl(B, v'= 3) molecules with He atoms in the expansion induce vibrational relaxation of the initially prepared dihalogen down to rotor states in the next lower ICl(B,v'= 2) level on timescales that compete with the rate for non-adiabatic transfer from the B state to the Z1 state. The resulting ICl(B,v'= 2,j') product rotational distribution, along with the analogous ICl(B,v'= 1,j') distribution formed by collisional relaxation of molecules in the long-lived ICl(B,v'= 2) level are compared to ICl(B,v'= 2,j') products formed by vibrational predissociation of He...ICl complexes prepared in different intermolecular vibrational levels within the He + ICl(B,v'= 3) potential. No evidence is observed for resonance-enhanced collisional cross sections, even at the low temperatures achieved, T < 1.0 K.

Laser-induced fluorescence spectra of Br(2) entrained in a He supersonic expansion have been recorded in the Br(2) B-X, 8-0, 12-0, and 21-0 spectral regions at varying downstream distances, and thus different temperature regimes. Features associated with transitions of the T-shaped and linear He...Br(2)(X,nu(") = 0) complexes are identified. The changes in the relative intensities of the T-shaped and linear features with cooling in the expansion indicate that the linear conformer is energetically more stable than the T-shaped conformer. A He + Br(2)(X,nu(") = 0) ab initio potential-energy surface, computed at the coupled cluster level of theory with a large, flexible basis set, is used to calculate the binding energies of the two conformers, 15.8 and 16.5 cm(-1) for the T-shaped and linear complexes, respectively. This potential and an excited-state potential [M. P. de Lara-Castells, A. A. Buchachenko, G. Delgado-Barrio, and P. Villareal, J. Chem. Phys. 120, 2182 (2004)] are used to calculate the excitation spectra of He...(79)Br(2)(X,nu(") = 0) in the Br(2) B-X, 12-0 region. The calculated spectra are used to make spectral assignments and to determine the energies of the excited-state intermolecular vibrational levels accessed in the observed transitions. Temperature-dependent laser-induced fluorescence spectra and a simple thermodynamic model [D. S. Boucher, J. P. Darr, M. D. Bradke, R. A. Loomis, and A. B. McCoy, Phys. Chem. Chem. Phys. 6, 5275 (2004)] are used to estimate that the linear conformer is 0.4(2) cm(-1) more strongly bound than the T-shaped conformer. Two-laser action spectroscopy experiments reveal that the binding energy of the linear He...(79)Br(2)(X,nu(") = 0) conformer is 17.0(8) cm(-1), and that of the T-shaped He...(79)Br(2)(X,nu(") = 0) conformer is then 16.6(8) cm(-1), in good agreement with the calculated values.

Laser-induced fluorescence and action spectroscopy experiments were performed to identify the origin of the Ar...I(2) continuum signals observed in and above the I(2) B-X spectral region. We have verified that these signals arise from transitions of the linear Ar...I(2) (X,v"=0) complex. The data provides no evidence that the excited state complexes undergo a one-atom caging mechanism when prepared above the I(2)(B) dissociation limit, Ar...I(2) (B)*-->Ar+I+I*-->Ar+I(2)(B,v'). Instead, our results indicate that the continuum signals result from bound-free transitions of the linear Ar...I(2) X,v(")=0) complex to the inner repulsive walls of numerous Ar+I(2)(B,v') intermolecular potentials. The bound-free continuum signal associated with transitions to each Ar+I(2)(B,v') potential spans an energy region >700 cm(-1). We have found that the continuum signals turn-on 250(2)cm(-1) above the corresponding I(2) B-X,v'-0 band origin, and this energy represents the binding energy of the linear Ar...I(2) (X,v"=0) conformer, D(0) (")(L)=250(2)cm(-1).

The He...I (35)Cl intermolecular vibrational levels with n'=0-6 that are bound within the He+ICl(B,v'=3) potential [A. B. McCoy, J. P. Darr, D. S. Boucher, P. R. Winter, M. D. Bradke, and R. A. Loomis, J. Chem. Phys. 120, 2677 (2004)] are identified in laser-induced fluorescence experiments performed at very low temperatures within a supersonic expansion. Comparisons of the positions and intensities of these lines with the excitation spectra, calculated using potential surfaces to describe the interactions between the helium atom and ICl in its ground and excited state, assist in the assignments. Based on these comparisons the excited state potential was rescaled so that the experimental and calculated J'=0 energies agree to within the experimental uncertainties for all but the lowest, n'=0, intermolecular level. Two-laser, action, and pump-probe spectroscopy experiments indicate that the bound He...I (35)Cl(B,v'=3) intermolecular vibrational levels undergo vibrational predissociation forming rotationally excited I (35)Cl(B,v'=2,j') products with distributions that depend upon the initial intermolecular vibrational level excited. Action spectra recorded in the ICl B-X, 2-0 region while monitoring the Deltav=0, I (35)Cl(B,v'=2) channel reveal two additional dissociation mechanisms for the He...I (35)Cl(B,v') excited state complexes: rotational predissociation of discrete metastable states lying slightly above the He+I (35)Cl(B,v'=2) asymptote and direct dissociation that occurs when the linear conformer is excited to the continuum of states above the same asymptote. The rotational predissociation pathway forms I (35)Cl(B,v'=2,j') products in all of the rotational states energetically accessible. The direct dissociation mechanism yields very cold rotational product state distributions; for instance, the average rotational energy in the product state distribution measured when the linear complexes are prepared 20 cm(-1) above the dissociation limit is only 1.51 cm(-1), representing only 7.6% of the available energy., ((c) 2005 American Institute of Physics.)

Transitions of two different stereoisomers of the He...ICl(X,v" = 0) weakly bound complex, one with a T-shaped orientation and another that is most likely linear, have been observed in laser-induced fluorescence experiments performed in the ICl B-X region. Here we present experimental and theoretical results aimed at confirming the previous assignments and at gaining additional insights into the He+ICl interactions. High resolution action spectra were recorded in the same region to identify those features that could be attributed to transitions of the He...I35Cl(X,v" = 0) isomers and not to higher-order complexes, Hen...I35Cl, where n > or = 2, or I37Cl containing species. Calculations of the rovibronic spectra of the He...I35Cl complexes in the ICl B-X, 2-0 and 3-0 regions were performed using an ab initio potential energy surface for the He+ICl(X,v" = 0) ground state and two different pairwise additive potentials for the He+ICl(B,v' = 2,3) excited states. The rotation-vibration energies and wave functions for the He cdots, three dots, centered I35Cl complexes were obtained for all bound states with total angular momentum J < 10 using both of these potentials. Electronic spectra were generated using these results, assuming that the transition moment lies along the ICl bond and is not perturbed by the presence of the helium atom. The calculations qualitatively reproduce the He cdots, three dots, centered I35Cl action spectrum and strongly support the previous assignments. The calculations also indicate that some of the spectral congestion observed near the linear band may be attributed to transitions of the linear isomer to multiple intermolecular levels in the excited state. Coriolis coupling strongly mixes He cdots, three dots, centered ICl(B,v') states with rotational excitation, making simulations and assignments of the linear band observed in the experimental spectrum difficult.

Differing caging mechanisms of electronically excited ICl within He...ICl complexes are investigated using laser-induced fluorescence and two-laser, pump-probe spectroscopy. A continuum signal is observed in laser-induced fluorescence spectra recorded with excitation energies that access regions above the I 2P3/2 + Cl 2P3/2 dissociation limit. We show that this signal is associated with transitions of the He ...ICl(X,v" = 0) complex with a linear equilibrium geometry to the continuum of states correlating with the repulsive, inner wall of the ICl(A 3pi1) potential. The dissociating ICl(A) molecule within the complex undergoes kinematic one-atom caging, ejecting the weakly bound He atom, and re-stabilizing the molecule in high lying vibrational levels within the A electronic state with very little rotational excitation. At higher excitation energies, weak LIF features superimposed on the continuum fluorescence signals are observed in preliminary investigations. When fixing an excitation laser on one of these features, at 18,012 cm(-1), I35Cl(B,v' = 2,3) vibrational levels are formed with little rotational excitation. This feature is associated with transitions of the linear He...I35Cl(X,v" = 0) complex to intermolecular states associated with the ICl(B) diabat that are coupled with those in the ICl(B') adiabat formed by an avoided curve crossing. The I35Cl(B,v') products are formed via a non-adiabatic one-atom caging mechanism of ICl* molecules within linear He...I35Cl* complexes.

Soluble CdSe quantum wires are prepared by the solution-liquid-solid mechanism, using monodisperse bismith nanoparticles to catalyze wire growth. The quantum wires have micrometer lengths, diameters in the range of 5-20 nm, and diameter distributions of +/-10-20%. Spectroscopically determined wire band gaps compare closely to those calculated by the semiemipirical pseudopotential method, confirming 2D quantum confinement. The diameter dependence of the quantum wire band gaps is compared to that of CdSe quantum dots and rods. Quantum rod band gaps are shown to be delimited by the band gaps of dots and wires of like diameter, for short and long rods, respectively. The experimental data suggest that a length of ca. 30 nm is required for the third dimension of quantum confinement to fully vanish in CdSe rods. That length is about six times the bulk CdSe exciton Bohr radius.

The size dependence of the bandgap is the most identifiable aspect of quantum confinement in semiconductors; the bandgap increases as the nanostructure size decreases. The bandgaps in one-dimensional (1D)-confined wells, 2D-confined wires, and 3D-confined dots should evolve differently with size as a result of the differing dimensionality of confinement. However, no systematic experimental comparisons of analogous 1D, 2D or 3D confinement systems have been made. Here we report growth of indium phosphide (InP) quantum wires having diameters in the strong-confinement regime, and a comparison of their bandgaps with those previously reported for InP quantum dots. We provide theoretical evidence to establish that the quantum confinement observed in the InP wires is weakened to the expected extent, relative to that in InP dots, by the loss of one confinement dimension. Quantum wires sometimes behave as strings of quantum dots, and we propose an analysis to generally distinguish quantum-wire from quantum-dot behaviour.

The entrance channel to the OH+H2-->H2O+H hydrogen abstraction reaction has been investigated from several different experimental approaches and complementary theoretical calculations. Weakly bound complexes between the hydroxyl radical and molecular hydrogen have been stabilized within a shallow well in the entrance channel and characterized via electronic spectroscopy on the OH A2Sigma+-X2Pi transition. Laser-induced fluorescence and fluorescence depletion experiments have revealed the binding energy of H2/D2 with ground state OH X2Pi radicals, the intermolecular energy levels supported by the OH A2Sigma+ (v'=0,1)+H2/D2 potential, and the OH-H2/D2 excited state dissociation limit. The OH X2Pi + H2 potentials have also been examined through inelastic scattering measurements on Lambda-doublet state-selected OH with normal or para-H2. Finally, photodetachment of an electron from the H3O- anion enabled the neutral reaction to be probed in conformations sampled by the two isomeric forms of the anion.

The branchio-oto-renal syndrome, first defined in 1976, is an autosomal dominant disorder characterized by anomalies of the external, middle, and inner ear in association with preauricular sinuses, branchial cleft anomalies, and varying degrees of renal dysplasia, including aplasia. Less frequently expressed phenotypic abnormalities include lacrimal duct aplasia and the stigmata of renal dysgenesis known as Potter facies. Although the precise incidence of the disorder is unknown, it may be more common than is generally appreciated and appears to be distinct from other autosomal dominant otobranchial syndromes. Features of the syndrome expressed in three members of a family are fully illustrated, and other reported cases are compared with these to emphasize the importance of prompt, comprehensive otologic, head and neck, uroradiologic, and genetic evaluation and management.