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.