Binding energy referencing for XPS in Alkali metal-based battery materials research (II): Application to complex composite electrodes

X-ray photoelectron spectroscopy (XPS) is a key method for studying (electro-)chemical changes in metal-ion battery electrode materials. In a recent publication, we pointed out a conflict in binding energy (BE) scale referencing at alkali metal samples, which is manifested in systematic deviations of the BEs up to several eV due to a specific interaction between the highly reactive alkali metal in contact with non-conducting surrounding species. The consequences of this phenomenon for XPS data interpretation are discussed in the present manuscript. Investigations of phenomena at surface-electrolyte interphase regions for a wide range of materials for both lithium and sodium-based applications are explained, ranging from oxide-based cathode materials via alloys and carbon-based anodes including appropriate reference chemicals. Depending on material class and alkaline content, specific solutions are proposed for choosing the correct reference BE to accurately define the BE scale. In conclusion, the different approaches for the use of reference elements, such as aliphatic carbon, implanted noble gas or surface metals, partially lack practicability and can lead to misinterpretation for application in battery materials. Thus, this manuscript provides exemplary alternative solutions

Theory of Vibrationally Inelastic Electron Transport through Molecular Bridges

Vibrationally inelastic electron transport through a molecular bridge that is connected to two leads is investigated. The study is based on a generic model of vibrational excitation in resonant transmission of electrons through a molecular junction. Employing methods from electron-molecule scattering theory, the transmittance through the molecular bridge can be evaluated numerically exactly. The current through the junction is obtained approximately using a Landauer-type formula. Considering different parameter regimes, which include both the case of a molecular bridge that is weakly coupled to the leads, resulting in narrow resonance structures, and the opposite case of a broad resonance caused by strong interaction with the leads, we investigate the characteristic effects of coherent and dissipative vibrational motion on the electron transport. Furthermore, the validity of widely used approximations such as the wide-band approximation and the restriction to elastic transport mechanisms is investigated in some detail.Comment: Submited to PRB, revised version according to comments of referees (minor text changes and new citations

Comparison of MODIS and VIIRS cloud properties with ARM ground-based observations over Finland

Cloud retrievals from the Moderate Resolution Imaging Spectroradiometer (MODIS) instruments aboard the satellites Terra and Aqua and the Visible Infrared Imaging Radiometer Suite (VIIRS) instrument aboard the Suomi-NPP satellite are evaluated using a combination of ground-based instruments providing vertical profiles of clouds. The ground-based measurements are obtained from the Atmospheric Radiation Measurement (ARM) programme mobile facility, which was deployed in Hyytiala, Finland, between February and September 2014 for the Biogenic Aerosols - Effects on Clouds and Climate (BAECC) campaign. The satellite cloud parameters cloud top height (CTH) and liquid water path (LWP) are compared with ground-based CTH obtained from a cloud mask created using lidar and radar data and LWP acquired from a multi-channel microwave radiometer. Clouds from all altitudes in the atmosphere are investigated. The clouds are diagnosed as single or multiple layer using the ground-based cloud mask. For single-layer clouds, satellites overestimated CTH by 326 (14 %) on average. When including multilayer clouds, satellites underestimated CTH by on average 169 m (5.8 %). MODIS collection 6 overestimated LWP by on average 13 g m(-2) (11 %). Interestingly, LWP for MODIS collection 5.1 is slightly overestimated by Aqua (4.56 %) but is underestimated by Terra (14.3 %). This underestimation may be attributed to a known issue with a drift in the reflectance bands of the MODIS instrument on Terra. This evaluation indicates that the satellite cloud parameters selected show reasonable agreement with their ground-based counterparts over Finland, with minimal influence from the large solar zenith angle experienced by the satellites in this high-latitude location.Peer reviewe

An efficient scheme for numerical simulations of the spin-bath decoherence

We demonstrate that the Chebyshev expansion method is a very efficient numerical tool for studying spin-bath decoherence of quantum systems. We consider two typical problems arising in studying decoherence of quantum systems consisting of few coupled spins: (i) determining the pointer states of the system, and (ii) determining the temporal decay of quantum oscillations. As our results demonstrate, for determining the pointer states, the Chebyshev-based scheme is at least a factor of 8 faster than existing algorithms based on the Suzuki-Trotter decomposition. For the problems of second type, the Chebyshev-based approach has been 3--4 times faster than the Suzuki-Trotter-based schemes. This conclusion holds qualitatively for a wide spectrum of systems, with different spin baths and different Hamiltonians.Comment: 8 pages (RevTeX), 3 EPS figure

Semiclassical Approximations in Phase Space with Coherent States

We present a complete derivation of the semiclassical limit of the coherent state propagator in one dimension, starting from path integrals in phase space. We show that the arbitrariness in the path integral representation, which follows from the overcompleteness of the coherent states, results in many different semiclassical limits. We explicitly derive two possible semiclassical formulae for the propagator, we suggest a third one, and we discuss their relationships. We also derive an initial value representation for the semiclassical propagator, based on an initial gaussian wavepacket. It turns out to be related to, but different from, Heller's thawed gaussian approximation. It is very different from the Herman--Kluk formula, which is not a correct semiclassical limit. We point out errors in two derivations of the latter. Finally we show how the semiclassical coherent state propagators lead to WKB-type quantization rules and to approximations for the Husimi distributions of stationary states.Comment: 80 pages, 4 figure

Basis set generation for quantum dynamics simulations using simple trajectory-based methods

Methods for solving the time-dependent Schrödinger equation generally employ either a global static basis set, which is fixed at the outset, or a dynamic basis set, which evolves according to classical-like or variational equations of motion; the former approach results in the well-known exponential scaling with system size, while the latter can suffer from challenging numerical problems, such as singular matrices, as well as violation of energy conservation. Here, we suggest a middle road: building a basis set using trajectories to place time-independent basis functions in the regions of phase space relevant to wave function propagation. This simple approach, which potentially circumvents many of the problems traditionally associated with global or dynamic basis sets, is successfully demonstrated for two challenging benchmark problems in quantum dynamics, namely, relaxation dynamics following photoexcitation in pyrazine, and the spin Boson model

Novel Cameras: Ultrathin mobile cameras with facet optics are maturing

Cameras that are based on the "insect eye" principle can be made half as thin as conventional smartphone cameras a new generation of these ultrathin cameras targets a resolution of 20 Mpixels