On the wavelength dependence of picosecond relaxation in crystal violet

The depopulation-repopulation kinetics of ground-state crystal violet in glycerol at room temperature has been investigated. A D₂O generated picosecond continuum served as a probe source and a 530 nm single pulse as an excitation source. The repopulation rate varies with probe wavelength; this dependence is ascribed to the presence of two rotamers of crystal violet.     

Uniqueness of the “nonsingular core” for Hermitian and other matrix pencils

Every pencil of hermitian matrices is conjunctive with a pencil of the form L ⊕ M, where L (the "minimal-indices" part) has no elementary divisors and M (the "nonsingular core") is a nonsingular pencil. Here it is shown that the conjunctivity type ofM is determined by that of L ⊕ M. The same method of proof applies to many other types of pencils, e.g. to congruence of pencils based on (1) a pair of symmetric matrices, (2) a pair of alternating matrices, or (3) a symmetric and an alternating matrix.     

UV photopatterning of a highly metallized, cluster-containing poly(ferrocenylsilane)

Thin films of a cobalt-clusterized poly(ferrocenylsilane) have been shown to behave as a negative-tone resist for UV photolithography, allowing access to feature sizes between 20 and 300 microm. Pyrolysis of the patterned polymer at 900 degrees C under a N(2) atmosphere afforded patterned ferromagnetic ceramics with excellent shape retention.     

Atomistic study of dislocation loop emission from a crack tip

We report the first atomistic calculation of the saddle-point configuration and activation energy for the nucleation of a 3D dislocation loop from a stressed crack tip in single crystal Cu. The transition state is found using reaction pathway sampling schemes, the nudged elastic band, and dimer methods. For the (111)[110] crack, loaded typically at 75% of the athermal critical strain energy release rate for spontaneous dislocation nucleation, the calculated activation energy is 1.1 eV, significantly higher than the continuum estimate. Implications concerning homogeneous dislocation nucleation in the presence of a crack-tip stress field are discussed.     

Water Spectra in the Region 4200-6250 cm, Extended Analysis of ν1+ν2, ν2+ν3, and 3ν2 Bands and Confirmation of Highly Excited States from Flame Spectra and from Atmospheric Long-Path Observations

Water vapor infrared spectra have been recorded at room temperature in the range 4200-6250 cm⁻¹ at resolutions (FWHM) between 0.0053 and 0.0080 cm⁻¹. The use of a White-type multireflection cell made large pressure × pathlength products possible up to 31.27 mbar×288.5 m. The high signal-to-noise ratio allowed us to observe lines with intensities as small as 10⁻²⁶ cm⁻¹/molecule cm⁻² at T=296 K. Among about 5100 recorded water lines, about half of which are reported for the first time, 2351 lines have been assigned to the second triad of H₂¹⁶O (bands ν₁+ν₂, ν₂+ν₃, and 3ν₂). This has allowed the determination of line positions and corresponding upper rovibrational states with considerably improved accuracy. The assignments of certain highly excited states have been confirmed by the analysis of flame spectra and hot emission spectra. New values of effective Hamiltonian parameters for the upper states {(110), (030), (011)} have been determined. The generating function model was used in the data reduction to account for the anomalously strong centrifugal distortion of the rovibrational levels and resonance interactions. The RMS standard deviation of the least-squares fit of the assigned H₂O data was 5×10⁻³ cm⁻¹ for line positions and 7×10⁻³ cm⁻¹ for energy levels up to J_max=20 and K_a(max)=13. Particular attention was paid to water lines in the transparency window 4200-5000 cm⁻¹, in which existing databases are not sufficient. In this region, 1395 lines of four isotopic species of water have been recorded and over 900 accurate line positions of nine bands of H₂¹⁶O (ν₁, ν₃, 2ν₂, ν₁+ν₂, ν₂+ν₃, 3ν₂, 4ν₂−ν₂, 2ν₂+ν₃−ν₂, ν₁+2ν₂−ν₂) are reported in this range. A comparison of laboratory spectra with long path atmospheric spectra (20 km slant path in the mountains) in this region shows that many lines missing from available spectroscopic compilations (or considerably shifted compared to observations) are important for a proper interpretation of atmospheric observations. A comparison of the observed data with the best available predictions from the molecular electronic potential energy surface is discussed.     

Likelihood Inferences for High-Dimensional Factor Analysis of Time Series With Applications in Finance

This article investigates likelihood inferences for high-dimensional factor analysis of time series data. We develop a matrix decomposition technique to obtain expressions of the likelihood functions and its derivatives. With such expressions, the traditional delta method that relies heavily on score function and Hessian matrix can be extended to high-dimensional cases. We establish asymptotic theories, including consistency and asymptotic normality. Moreover, fast computational algorithms are developed for estimation. Applications to high-dimensional stock price data and portfolio analysis are discussed. The technical proofs of the asymptotic results and the computer codes are available online.     

Tunable light‐harvesting polymers containing embedded dipolar chromophores for polymer solar cell applications

A series of light‐harvesting conjugated polymers were designed and synthesized for polymer solar cells. These newly designed polymers comprise an unusual two‐dimensional conjugated structure with an electron‐rich thiophene–triphenylamine backbone and stable planar indacenodithiophene π‐bridges terminated with tunable electron acceptors. It was found that the electron‐withdrawing strength of the acceptor could be used to manipulate the energy level of the lowest unoccupied molecular orbital and bandgap (as much as 0.3 eV), generating derivatives with complementary absorbance in the visible spectrum. This approach provides great flexibility in fine tuning the electronic and optical properties of the resultant polymers and facilitates the investigation of how these chemical modifications alter the subsequent photovoltaic properties of these materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Sensitized phosphorescence: a gas phase molecular mixing diagnostic

The use of sensitized phosphorescence for visualization of gas phase fluid mixing and the requirements for quantitative imaging measurements are discussed. A model for estimating the molecular-mixing signal's dependence on fluid composition is developed and candidate molecular reactants are considered within the framework of the model. Experiments based on sensitized phosphorescence from both an acetonebiacetyl system and a toluene-biacetyl system show good qualitative agreement with modeled results. It is concluded that quantitative measurements using sensitized phosphorescence are feasible.     

A soft matter in construction – Statistical physics approach to formation and mechanics of C–S–H gels in cement

Calcium-silicate hydrate (C–S–H) is the main binding agent in cement and concrete. It forms at the beginning of cement hydration, it progressively densifies as cement hardens and is ultimately responsible of concrete performances. This hydration product is a cohesive nano-scale gel, whose structure and mechanics are still poorly understood, in spite of its practical importance. Here we review some of the open questions for this fascinating material and a statistical physics approach recently developed, which allows us to investigate the gel formation under the out-of-equilibrium conditions typical of cement hydration and the role of the nano-scale structure in C–S–H mechanics upon hardening. Our approach unveils how some distinctive features of the kinetics of cement hydration can be related to changes in the morphology of the gels and elucidates the role of nano-scale mechanical heterogeneities in the hardened C–S–H.