A sequential molecular mechanics/quantum mechanics study of the electronic spectra of amides

We report gas-phase electronic spectra of formamide, N-methyformamide, acetamide, and N-methylacetamide at 300 K calculated using a combination of classical molecular dynamics and time-dependent density functional theory (TDDFT). In comparison to excitation energies computed using the global minima structures, the valence npi* and pi(nb)pi* states show a significant red-shift of 0.1-0.35 eV, while smaller shifts are found for the n3s and pi(nb)3s Rydberg states. In this work, we have identified the physical origin of these shifts arising from variations of the molecular structure. We present simple relationships between key geometrical parameters and spectral shifts. Consequently, electronic spectra can be generated directly from ground-state structures, without additional quantum chemical calculations. The electronic spectrum of formamide in aqueous solution is computed using TDDFT using an explicit solvent model. This provides a quantitative determination of the condensed-phase spectrum. In general, this study shows that temperature effects can change the predicted excitation energies significantly and demonstrates how electronic spectra at elevated temperatures can be computed in a computationally efficient way.     

Singular solutions of elliptic equations on a perturbed cone

In this work we obtain positive singular solutions of

$\{\begin{array}{ccc}?\mathrm{\Delta }u(y)\hfill & \hfill =\hfill & u{(y)}^p\text{ in }y\in {\mathrm{\Omega }}_t,\hfill \\ u\hfill & \hfill =\hfill & 0\text{ on }y\in ?{\mathrm{\Omega }}_t,\hfill \end{array}$

where ${\mathrm{\Omega }}_t$ is a sufficiently small $C^{2,\alpha }$ perturbation of the cone $\mathrm{\Omega }:=\{x\in {\mathbb{R}}^N:x=r\theta ,r>0,\theta \in S\}$ where $S?S^{N?1}$ has a smooth nonempty boundary and where $p>1$ satisfies suitable conditions. By singular solution we mean the solution is singular at the ‘vertex of the perturbed cone’. We also consider some other perturbations of the equation on the unperturbed cone Ω and here we use a different class of function spaces.     

Mesoscopic phase statistics of diffuse ultrasound in dynamic matter

Temporal fluctuations in the phase of waves transmitted through a dynamic, strongly scattering, mesoscopic sample are investigated using ultrasonic waves, and compared with theoretical predictions based on circular Gaussian statistics. The fundamental role of phase in diffusing acoustic wave spectroscopy is revealed, and phase statistics are also shown to provide a sensitive and accurate way to probe scatterer motions at both short and long time scales.     

Photocatalytic Water Oxidation by a Pyrochlore Oxide upon Irradiation with Visible Light: Rhodium Substitution Into Yttrium Titanate

A stable visible‐light‐driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y₂Ti₂O₇ is demonstrated by monitoring Vegard′s law evolution of the unit‐cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible‐light active. The overall rate of oxygen evolution is comparable to WO₃ but with superior light‐harvesting and surface‐area‐normalized turnover rates, making Y₂Ti_1.94Rh_0.06O₇ an excellent candidate for use in a Z‐scheme water‐splitting system.     

The photoelectron spectrum of thiazyl fluoride (NSF)

The photoelectron spectrum of thiazyl fluoride has been recorded. An assignment of the first five bands has been attempted, using semi-empirical calculations.     

Artificial polarization anomalies from holographic gratings

An aluminum reflection grating made holographically was found to display polarization anomalies when illuminated with p-polarized light. Additional anomalies were detected for both p- and s-polarizations after the grating was coated with a layer of dielectric (410 nm of photoresist). These new anomalies have been interpreted in terms of the optical guided modes of a thin film dielectric waveguide bounded on one side by metal and on the other by vacuum.     

Synthetic metals based on tetramethyltetraselenafulvalene(TMTSF): Varied anisotropy in the low temperature (125K) structures of (TMTSF)2X,X=C104-, PF6-, and AsF6-.

The low temperature (125K) X-ray crystal structures of (TMTSF)₂X, X=C10₄^-, PF₆^-, and AsF₆^- reveal decreases in the intermolecular interand intrastack Se-Se contact distances upon cooling (298K to 125K) which are highly anisotropic and different from one salt to another. The changes in the interstack distances, which are normal to the stacking direction, are approximately twice those involving intrastack Se-Se interactions. These observations establish that the anisotropic structural changes which accompany decreased temperature are common to numerous (TMTSF)₂X radical cation conducting salts.     

In memory of V.I. Zaborov (March 16, 1927–August 30, 2004)

Chronicle

In memory of V.I. Zaborov (March 16, 1927–August 30, 2004)     

Improved direct measurement of the parity-violation parameter Ab using a mass tag and momentum-weighted track charge

We present an improved direct measurement of the parity-violation parameter A(b) in the Z boson-b-quark coupling using a self-calibrating track-charge technique applied to a sample enriched in Z-->bb events via the topological reconstruction of the B hadron mass. Manipulation of the Stanford Linear Collider electron-beam polarization permits the measurement of A(b) to be made independently of other Z-pole coupling parameters. From the 1996-1998 sample of 400,000 hadronic Z decays, produced with an average beam polarization of 73.4%, we find A(b)=0.906+/-0.022(stat)+/-0.023(syst).     

An extension of Tanner's results on uncontrolled intersections

A delay formula is developed for the problem, analyzed by Tanner in 1962, where two streams of traffic have conflicting demands at an intersection. The situation is such that the major stream has absolute priority and the minor stream vehicles can only enter the intersection when sufficiently large gaps appear in the major stream. This paper extends Tanner's work by considering a generalised stochastic structure on the arrival streams. The paper also links Tanner's work to other papers of this author where the utilitarian value of this generalised model has been established in a wide range of traffic problems.