Non-adiabatic Effects in the Dissociation of Oxygen Molecules at the Al(111) Surface

The measured low initial sticking probability of oxygen molecules at the Al(111) surface that had puzzled the field for many years was recently explained in a non-adiabatic picture invoking spin-selection rules [J. Behler et al., Phys. Rev. Lett. 94, 036104 (2005)]. These selection rules tend to conserve the initial spin-triplet character of the free O2 molecule during the molecule's approach to the surface. A new locally-constrained density-functional theory approach gave access to the corresponding potential-energy surface (PES) seen by such an impinging spin-triplet molecule and indicated barriers to dissociation which reduce the sticking probability. Here, we further substantiate this non-adiabatic picture by providing a detailed account of the employed approach. Building on the previous work, we focus in particular on inaccuracies in present-day exchange-correlation functionals. Our analysis shows that small quantitative differences in the spin-triplet constrained PES obtained with different gradient-corrected functionals have a noticeable effect on the lowest kinetic energy part of the resulting sticking curve.Comment: 17 pages including 11 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Changes of vibrational lifetimes with minor structural modification of small polyatomic molecules

Substantial changes of population lifetimes of CH-stretching modes are observed when two atoms are exchanged in CH2=CCl2 to form trans CHCl=CHCl and when three deuterons are substituted in C6H6 to form 1,3,5.-C6H3D3. The measured lifetimes are in good agreement with estimates based on Fermi resonance-mixing which is inferred from infrared and Raman spectra

A new Raman technique of superior spectral resolution

Raman-active vibrational modes are coherently excited by the transient stimulated Raman process. A subsequent delayed probe of relatively long duration interacts with the freely relaxing vibrations. Raman spectra are generated with higher resolution and more accurate peak positions than in conventional Raman spectroscopy. In liquid cyclohexane four new Raman lines were readily detected in the frequency range 2870–2920 cm−1

Optimal Topological Test for Degeneracies of Real Hamiltonians

We consider adiabatic transport of eigenstates of real Hamiltonians around loops in parameter space. It is demonstrated that loops that map to nontrivial loops in the space of eigenbases must encircle degeneracies. Examples from Jahn-Teller theory are presented to illustrate the test. We show furthermore that the proposed test is optimal.Comment: Minor corrections, accepted in Phys. Rev. Let

On-chip spectroscopy with thermally-tuned high-Q photonic crystal cavities

Spectroscopic methods are a sensitive way to determine the chemical composition of potentially hazardous materials. Here, we demonstrate that thermally-tuned high-Q photonic crystal cavities can be used as a compact high-resolution on-chip spectrometer. We have used such a chip-scale spectrometer to measure the absorption spectra of both acetylene and hydrogen cyanide in the 1550 nm spectral band, and show that we can discriminate between the two chemical species even though the two materials have spectral features in the same spectral region. Our results pave the way for the development of chip-size chemical sensors that can detect toxic substances

CO oxidation at Pd(100): A first-principles constrained thermodynamics study

The possible formation of oxides or thin oxide films (surface oxides) on late transition metal surfaces is recently being recognized as an essential ingredient when aiming to understand catalytic oxidation reactions under technologically relevant gas phase conditions. Using the CO oxidation at Pd(100) as example, we investigate the composition and structure of this model catalyst surface over a wide range of (T,p)-conditions within a multiscale modeling approach where density-functional theory is linked to thermodynamics. The results show that under the catalytically most relevant gas phase conditions a thin surface oxide is the most stable "phase" and that the system is actually very close to a transition between this oxidic state and a reduced state in form of a CO covered Pd(100) surface.Comment: 13 pages including 7 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

A joint time-dependent density-functional theory for excited states of electronic systems in solution

We present a novel joint time-dependent density-functional theory for the description of solute-solvent systems in time-dependent external potentials. Starting with the exact quantum-mechanical action functional for both electrons and nuclei, we systematically eliminate solvent degrees of freedom and thus arrive at coarse-grained action functionals which retain the highly accurate \emph{ab initio} description for the solute and are, in principle, exact. This procedure allows us to examine approximations underlying popular embedding theories for excited states. Finally, we introduce a novel approximate action functional for the solute-water system and compute the solvato-chromic shift of the lowest singlet excited state of formaldehyde in aqueous solution, which is in good agreement with experimental findings.Comment: 11 page

Graph Convolutional Networks for Model-Based Learning in Nonlinear Inverse Problems

The majority of model-based learned image reconstruction methods in medical imaging have been limited to uniform domains, such as pixelated images. If the underlying model is solved on nonuniform meshes, arising from a finite element method typical for nonlinear inverse problems, interpolation and embeddings are needed. To overcome this, we present a flexible framework to extend model-based learning directly to nonuniform meshes, by interpreting the mesh as a graph and formulating our network architectures using graph convolutional neural networks. This gives rise to the proposed iterative Graph Convolutional Newton-type Method (GCNM), which includes the forward model in the solution of the inverse problem, while all updates are directly computed by the network on the problem specific mesh. We present results for Electrical Impedance Tomography, a severely ill-posed nonlinear inverse problem that is frequently solved via optimization-based methods, where the forward problem is solved by finite element methods. Results for absolute EIT imaging are compared to standard iterative methods as well as a graph residual network. We show that the GCNM has strong generalizability to different domain shapes and meshes, out of distribution data as well as experimental data, from purely simulated training data and without transfer training

Ab initio Molecular Dynamics in Adaptive Coordinates

We present a new formulation of ab initio molecular dynamics which exploits the efficiency of plane waves in adaptive curvilinear coordinates, and thus provides an accurate treatment of first-row elements. The method is used to perform a molecular dynamics simulation of the CO_2 molecule, and allows to reproduce detailed features of its vibrational spectrum such as the splitting of the Raman sigma+_g mode caused by Fermi resonance. This new approach opens the way to highly accurate ab initio simulations of organic compounds.Comment: 11 pages, 3 PostScript figure